Pilot installation for the thermo-chemical characterisation of solid wastes

The increasing production and the large variety of wastes require operators of thermal treatment units to continuously adapt the installations or the functioning parameters to the different physical and chemical properties of the wastes. Usually, the treated waste is encountered in the form of heterogeneous mixtures. The classical tests such as thermogravimetry and calorimetric bomb operate component by component, separately. In addition to this, they can analyse only small quantities of waste at a time (a few grams). These common tests are necessary but insufficient in the global waste analysis in the view further thermal treatment. This paper presents an experimental installation, which was designed and built at the CNRS Science Division, Department of Industrial Methods, Compiègne University of Technology, France. It allows the determination of waste thermal and chemical properties by means of thermal treatment. Also, it is capable of continuously analysing significant quantities of waste (up to 50kg/h) as compared to the classical tests and it can work under various conditions: The installation reproduces the process conditions from incinerators or pyrolysis reactors. It also provides complete information on the kinetics of the waste thermal degradation and on the pollutant emissions. Using different mixtures of components present in the municipal solid waste and also in the reconstituted MSW samples, we defined a series of criteria for characterising waste behaviour during the stages of the main treatment process such as: feeding, devolatilisation/oxidation, advancement, solid residue evacuation, and pollutants emission.     

Leachate recirculation effects on waste degradation: study on columns

The purpose of this study is to determine the impact of leachate recirculation on the degradation of municipal solid wastes (bioreactor concept). The study was carried out using columns containing approximately 50 kg of waste, in order to follow waste degradation over a limited time. Three types of waste were studied: fresh waste of standard composition, fresh waste of fermentable composition and some 8-yr-old waste extracted from a site in France. Measurement of the global parameters, such as chemical oxygen demand (COD), volatile acidity, alkalinity, leachate conductivity, methane potential of the wastes and biogas production monitoring (volume of CO2 and CH4 produced), were carried out. The quantity of oxydizable matter and biogas production was increased by the leachate recirculation, and the duration of the first degradation phases was reduced in all cases. Chloride, ammonium and organic pollution accumulation was observed according to the duration of recirculation. After 400 days of degradation, waste stabilization seemed to be reached for all of the recirculated columns (COD<300 mg/L O2, and methane potential reached).     

Evaluation of commercial landscaping mulch for possible contamination from CCA

Wood treated with chromated copper arsenate (CCA) is found in construction and demolition (C&D) debris, and a common use for wood recycled from C&D debris is the production of mulch. Given the high metals concentrations in CCA-treated wood, a small fraction of CCA-treated wood can increase the metal concentrations in the mulch above regulatory thresholds. The objective of this study was to determine the extent of contamination of CCA-treated wood in consumer landscaping mulch and to determine whether visual methods or rapid X-ray fluorescence (XRF) technology can be used to identify suspect mulch. Samples were collected throughout the State of Florida (USA) and evaluated both visually and chemically. Visual analysis focused on documenting wood-chip size distribution, whether the samples were artificially colored, and whether they contained plywood chips which is an indication that the sample was, in part, made from recycled C&D wood. Chemical analysis included measurements of total recoverable metals, leachable metals as per the standardized synthetic precipitation leaching procedure (SPLP), and XRF analysis. Visual identification methods, such as colorant addition or presence of plywood, were found effective to preliminarily screen suspect mulch. XRF analysis was found to be effective for identifying mulch containing higher than 75 mg/kg arsenic. For mulch samples that were not colored and did not contain evidence of C&D wood, none exceeded leachable metal concentrations of 50 microg/L and only 3% exceeded 10 mg/kg for recoverable metals. The majority of the colored mulch made from recycled C&D wood contained from 1% to 5% CCA-treated wood (15% maximum fraction) resulting in leachable metals in excess of 50 microg/L and total recoverable metals in excess of 10 mg/kg. The maximum arsenic concentration measured in the mulch samples evaluated was 230 mg/kg, which was above the Florida residential direct exposure regulatory guideline of 2.1 mg/kg.     

Removal of aqueous lead by poorly-crystalline hydroxyapatites

The use of a phosphorus amendment in altering Pb to a chemically less mobile phase is a promising strategy based on minimizing ecotoxicological risk and improving time and cost efficiency. This study evaluated crystalline and poorly-crystalline hydroxyapatite sorbents on removal of aqueous Pb in response to reaction time, solution pH, and Pb concentration. Batch experiments were conducted using a commercially-available crystalline hydroxyapatite (HA), and two poorly-crystalline hydroxyapatites synthesized from gypsum waste (CHA) and incinerated ash of poultry waste (MHA). Poorly-crystalline hydroxyapatites had greater capacity for Pb removal from a solution with a wider pH range as compared to a crystalline hydroxyapatite. The maximum sorption capacity of Pb determined by the Langmuir model was 500 mg g⁻¹ for CHA, 277 mg g⁻¹ for MHA and 145 mg g⁻¹ for HA. Removal of aqueous Pb by CHA was not dependent on solution pH, with a 98.8% reduction throughout the solution pH range of 2–9, whereas aqueous Pb removal by HA and MHA was pH-dependent with less removal in the neutral solution pH. Poorly-crystalline hydroxyapatites may provide an effective alternative to existing remediation technologies for Pb-contaminated sites.     

Evaluating the fish safety level of river water and wastewater with a larval medaka assay

A larval medaka (Oryzias latipes) assay was proposed to evaluate the fish safety level of river waters and wastewaters. Organic toxicants were 10-100 times concentrated with adsorption cartridges from 4 l of river water or 1-10 times concentrated from 400 ml of wastewater. Toxicity of these concentrated solutions was determined by exposing 48-72 h post-hatch age larvae for 48 h. The method effectively revealed a variation of the median lethal concentration ratio (LCR50) from 13 to >100 in 125 river water samples, and from <1 to >10 in five typical wastewater samples. Ayase River, which takes water mostly from agricultural or household discharge, showed significantly (P<0.001) lower LCR50 than Sagami River that takes natural water as the source. Safety Levels in both Sagami River and Ayase River were influenced by the irrigation activity, LCR50 at some sites showing a seasonal-specific decrease in winter. Pollution from pulp and paper industries contributed to the low LCR50 in several tributaries of Ayase River. Required little manpower in sampling, pretreatment and testing, the proposed larval medaka assay was proved as an efficient tool for screening those high risk sites for priority management.     

Evaluation of Point and Diffuse Sources of Nutrients in a River Basin on Base of Monitoring Data

The methodology of materials accounting is presented and applied to developing nutrient balance (nitrogen and phosphorus) in a river basin. The method is based on the balance principle: inputs and outputs of each nitrogen and phosphorus related sub-systems were balanced. The application of the methodology strategies was illustrated by means of a case study of the Krka river, Slovenia. Different pathways of emission to surface waters were taken into account: WWTP discharges, direct discharges, erosion/runoff and baseflow. Total annual emission into the river Krka was estimated to be 362 tonnes N/year and 73.3 tonnes P/year. The main sources of nitrogen are diffuse sources, emitted via baseflow (52%). Other important sources are effluents from WWTP, which account for 36% of total emissions. Other sources like erosion and direct discharges to surface water (animal manure, industry, households) are of lower magnitude. Erosion is main source of phosphorus emission (55% of total emission), WWTP effluents account for 37% of total emission, while other sources are less important. Besides reduction of point sources by means of wastewater collection and implementation of nutrient removal technology, managing agricultural nitrogen and phosphorus to protect water quality should become a major challenge in the Krka river basin.     

Comparison of organochlorine compound concentrations in colostrum and mature milk

Human breast milk represents the best choice for the nutrition of infants. It is often used for monitoring human exposures to environmental chemicals. Uniquely suited to meet human biological needs, breast milk composition, especially fat content, changes significantly with time from delivery. With the aim to compare the concentration of organochlorine compounds (OCs) in colostrum versus mature milk, we obtained samples of fourth-fifth day postpartum milk (colostrum) and day-14 postpartum milk (mature milk) from 12 women enrolled in the project "Early Childhood Development and PCB Exposure in Slovakia". The concentrations of selected organochlorine pesticides and congeners of polychlorinated biphenyls (PCBs) were measured using gas chromatography with electron capture detection and reported on lipid adjusted basis. No significant differences were found between organochlorine levels in colostrum and those in mature milk samples. A very close correlation was found between the concentrations of organochlorine compounds in colostrum and mature milk (Spearman correlation coefficient r=0.94-0.98 for PCBs, and r=0.85-0.99 for organochlorine pesticides, p<0.001 for all compounds). The present study concludes that the use of colostrum samples provides a close estimate of the child's exposure to OCs in the early neonatal period and demonstrates that, despite the lower fat content, colostrum specimens are adequate to conduct OC analyses.     

Remediation of cadmium-contaminated paddy soils by washing with chemicals: effect of soil washing on cadmium uptake by soybean

We conducted a pot experiment to evaluate the effect of soil washing with CaCl(2) on Cd absorption by two soybean cultivars. The results were as follows: (1) Soybean growth was not significantly different in washed and unwashed soils, but the seed Cd concentration for both cultivars decreased significantly, up to 25%, in the washed soils compared with the unwashed soils. (2) In the washed soils, the Cd concentration in the soil solution indicated an obviously lower value from sowing to the flowering stage; however, the change in Cd speciation was not evident in the CaCl(2)-washed soil solution. Consequently, the effect of soil washing using CaCl(2) on Cd-contaminated paddy soils can be expected to continue after a CaCl(2)-washed paddy field is converted to an upland field.     

The fate of isoproturon in a freshwater microcosm with Lemna minor as a model organism

Degradation, bioaccumulation and volatile loss of the 14C-labeled phenylurea herbicide isoproturon (IPU) was examined in a freshwater microcosm with the free floating macrophyte species Lemna minor during a 21-day exposure time. Isoproturon volatilisation was very low with 0.13+/-0.01% of the initially applied herbicide. Only a minor amount of the herbicide was completely metabolised, presumably by rhizosphere microorganisms and released as 14CO2. In total, about 9% isoproturon was removed from the aquatic medium during 21 days. The major portion of the pesticide was removed by bioaccumulation of Lemna minor (5.0+/-0.8%) and the bioconcentration factor (BCF) based on freshweight was 15.8+/-0.2. However, this study indicated a high persistence of IPU in freshwater ecosystems and a potential hazard due to bioaccumulation in non-target species. The novel experimental system of this study, developed for easy use and multiple sampling abilities, enabled quantitatively studying the fate of isoproturon and showed high reproducibility with a mean average (14)C-recovery rate of 97.1+/-0.7%.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.