Platinum emission rate of automobiles with catalytic converters

Inconsistent data presently available on the platinum emission rate of cars in Germany equipped with catalytic converters are evaluated. Automobile sources of Pt other than autocatalysts are quantified and found to be 1–6 orders of magnitudes lower than the Pt emissions attributed to catalytic converters. A transfer of emission rates derived from test stand experiments to more realistic street conditions reaches 0.8 μg Pt/km. In this manner, data from test stand experiments and from environmental investigations meet in the range of 0.5–0.8 μg Pt/km.     

Studies on reactions of ozone with alkenes

In the last years, a continuous increase of the O3 concentration has been recorded in the lower atmospheric layers. Photochemical reactions with NO(x), CO and organic compounds are the main sources of O3 in the troposphere. In this work, an attempt was made to determine the impact of alkenes on the O3 concentration in the troposphere. A study on the gas-phase reactions of 03 with 1-hexene, 1-heptene and 1-nonene was made. The reactions were carried out at room temperature under atmospheric pressure. Ozone was formed by the ultraviolet radiation emitted by a mercury lamp, in order to simulate the atmospheric conditions. The changes with time in the concentration of O3, 1-alkenes and formed aldehydes were investigated. Qualitative and quantitative analyses were done by means of the gas chromatography and colorimetry. The following products were identified: pentanal from 1-hexene; hexanal from 1-heptene; oktanal from 1-nonene. For each of the reactions, HCHO was also determined as a product. The reaction rate constants were calculated and obtained in units of 10(-17) cm(-3) molecule(-1) s(-1): 1.94-0.99 for 1-hexene, 5.54-4.51 for 1-heptene and 1.54-0.76 for 1-nonene. Based on the results obtained, an explanation of O3 concentration variations in the planetary boundary layer can be given. Last year a considerable increase of O3 concentration on the roads of Western Europe was recorded. This increase could have resulted from the decrease of alkene concentration in the air due to common use of the catalytic converters in cars. The unsaturated hydrocarbons rapidly oxidize on the catalyst. In Eastern Europe, where the amount of cars equipped with catalytic converters is smaller than in Western Europe, the alkene content in the exhaust fumes results in a decrease of the O3 concentration in the troposphere.     

Accumulation and distribution of platinum and rhodium in the European eel Anguilla anguilla following aqueous exposure to metal salts

The platinum group metals (PGM) Pt and Rh are emitted into the environment mainly by catalytic exhaust gas converters of cars and by effluents of hospitals, which use Pt based anti-cancer drugs. However, there is still a lack of information on the availability of these precious metals to the biosphere. As PGM accumulate in sediments of aquatic ecosystems we focused our study on the uptake of the noble metals by European eels, Anguilla anguilla. Therefore, eels were exposed in tap water and humic water containing Pt(4+) and Rh(3+) at a concentration of 170 and 260 microg/l, respectively. After an exposure period of 6 weeks the mean Pt levels in bile, liver, kidney and intestine of the exposed eels ranged between 68 ng/g and 840 ng/g and the mean Rh levels between 35 ng/g and 155 ng/g whereas the PGM levels of the unexposed controls were below the detection limit of 50 ng/g for Pt and 5 ng/g for Rh. Rh was also taken up by gill and spleen. No PGM uptake was found for muscle and blood. The pattern of metal distribution within the eel differed between Pt and Rh and was dependent on the water type. Due to their accumulation capacity for PGM eels are suitable as accumulation indicators to detect PGM pollution in aquatic ecosystems.     

Atmospheric deposition, retention, and stream export of dioxins and PCBs in a pristine boreal catchment

The mass-balance between diffuse atmospheric deposition of organic pollutants, amount of pollutants retained by the terrestrial environment, and levels of pollutants released to surface stream waters was studied in a pristine northern boreal catchment. This was done by comparing the input of atmospheric deposition of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and PCBs with the amounts exported to surface waters. Two types of deposition samplers were used, equipped with a glass fibre thimble and an Amberlite sampler respectively. The measured fluxes showed clear seasonality, with most of the input and export occurring during winter and spring flood, respectively. The mass balance calculations indicates that the boreal landscape is an effective sink for PCDD/Fs and PCBs, as 96.0-99.9 % of received bulk deposition was retained, suggesting that organic pollutants will continue to impact stream water in the region for an extended period of time.     

Persistence and fate of polychlorinated biphenyls (PCBs) in sewage sludge-amended agricultural soils

Four metal enriched sewage sludges containing different concentrations of polychlorinated biphenyls (PCBs) were applied to two field soils in the UK in 1968. Samples of the sludges, sludge-amended soils and soils from untreated control plots were stored and analysed retrospectively. Sludge concentrations ranged from 1 to 7 mg SigmaPCB kg(-1). The pattern of PCBs was similar in three of the four sludges, with congeners 14, 18, 28 and 52 present at the highest concentrations. The fourth sludge contained higher amounts of congeners 149, 153, 138 and 180. SigmaPCB concentrations in control plot soil have declined over the last 20 years, indicating a reduction in atmospheric deposition inputs of PCBs to the soil. SigmaPCB concentrations also declined on the sludge-amended plots, reaching control plot concentrations (30-60 microg SigmaPCB kg(-1)) in the late-1980s. Half-lives ranged from < 1 to 8.5 years for congeners 18, 28 and SigmaPCB. Biodegradation and/or the formation of reversibly sorbed soil PCB residues could not account for the losses observed. Volatilisation is implicated as the most important loss process on both the control and sludge-amended plots. Using the fugacity approach, congener concentrations in soils at Luddington were predicted still to have not reached equilibrium with the air. Further losses to the atmosphere are likely.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in urban and suburban areas of Korea

Bulk atmospheric samples (wet and dry) were collected monthly throughout a year at urban and suburban areas of Korea to assess the deposition flux and seasonal variations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The PCDDs/DFs deposition fluxes ranged from 1.0 to 3.7 ng TEQ/m²/year in the urban area and from 0.5 to 4.6 ng TEQ/m²/year in the suburban area. The deposition fluxes of PCDDs/DFs in this study were comparable to or lower than those previously reported at different locations. The atmospheric deposition fluxes of particles and PCDDs/DFs in winter tended to be higher than those in summer. However, monthly variations between particle and PCDDs/DFs deposition fluxes were small, and the correlation coefficients between the deposition fluxes of air particles and each homologue group of PCDDs/DFs varied according to the degree of chlorination of the homologue group. The deposition velocity of PCDDs/DFs in the urban area was estimated at 0.04 cm/s, which is a lower value than those found in other studies. The two most likely factors affecting the monthly variation of deposition fluxes are the ambient temperature and the amount of precipitation. In particular, the ambient temperature had an influence on the lower chlorinated homologues of PCDDs/DFs while precipitation had an influence on the higher chlorinated PCDDs/DFs. The PCDDs/DFs profiles in atmospheric deposition bulk samples showed a similar pattern at the urban and suburban sites. The possibility of the loading of PCDDs/DFs by Asian dust events could be partly confirmed by investigation of homologue profiles.     

The acanthocephalan Paratenuisentis ambiguus as a sensitive indicator of the precious metals Pt and Rh from automobile catalytic converters

Recent studies revealed that intestinal acanthocephalans of fish can accumulate heavy metals to concentrations orders of magnitude higher than those in the host tissues or the aquatic environment. This significant heavy metal accumulation by acanthocephalans, even surpassing that of established free living accumulation bioindicators, encouraged us to study the bioavailability of the platinum-group-metals (PGM) Pt and Rh for parasites. These precious metals are used in catalytic converters of cars for exhaust gas purification in Europe since the early 1980s. In addition to the beneficial effect in reducing the emission of CHx, CO and NOx of cars there is an increasing emission of these metals. However, it still remains unclear if these elements become accumulated in the biosphere and whether they affect the health of organisms. The present study reveals that in European eels (Anguilla anguilla) naturally infected with the eoacanthocephalan parasite Paratenuisentis ambiguus and experimentally exposed to ground catalytic converter material, the parasites take up and accumulate the catalytic active metals Pt and Rh whereas in the examined host tissues we found no metal uptake. Compared with the PGM concentrations in the water the worms contained 1600 times higher Rh and 50 times higher Pt concentrations. Thus, the parasites can be used as sentinel organisms reflecting even very low levels of precious metals.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.     

Nitro musks, nitro musk amino metabolites and polycyclic musks in sewage sludges. Quantitative determination by HRGC-ion-trap-MS/MS and mass spectral characterization of the amino metabolites

Nitro- and polycyclic musks were quantified in sewage sludge samples from different catchment areas using high-resolution gas chromatography (HRGC) and ion-trap MS/MS. Collision induced dissociation (CID) turned out to be a useful tool for quantification of the analytes. Negative chemical ionization (NCI) quadrupole MS in the selected ion mode (SIM) showed similar sensitivities compared to ion trap MS/MS. Among the nitro musks, musk ketone (MK) and musk xylene (MX) were the main compounds in predominantly domestic sewage sludges, found at low microgram/kg dry matter (d.m.) whereas polycyclic musks were present in domestic as well as in industrial sludges up to 12 mg/kg d.m. Galaxolide (HHCB) and Tonalide (AHTN) were the major polycyclic musks found in the sludges. Amino metabolites of the nitro musks, amino musk xylene (AMA), amino musk moskene (AMM) and amino musk ketone (AMK) were detected for the first time in sewage sludges, and reached partly higher concentrations compared to the parent compounds.     

Determination of coplanar and ortho substituted PCBs in some sewage sludges of Switzerland using HRGC/ECD and HRGC/MSD

The three most toxic coplanar PCB congeners PCB 77, 126 and 169 as well as 7 mono-and di-ortho-PCBs (PCB 28, 52, 101, 118, 153, 138, 180) were measured in 19 sewage sludges. Concentrations of the coplanar PCBs ranged between 231–5050 ng/kg dw for PCB 77, 43–1511 ng/kg dw for PCB 126 and 29–273 ng/kg dw for PCB 169. Comparable results were obtained with mass selective detection in the single ion monitoring mode (MSD-SIM) except for PCB 169, where MSD-SIM was less sensitive than ECD. The sum of the 7 mono-and di-ortho-PCBs, which are routinely measured as representatives of the PCB fraction, reached levels between 43–550 μg/kg dw and agreed well with results previously obtained in our laboratory. Based on our data, a selective accumulation of the coplanar PCBs could not be observed. Sludges that received industrial effluents clearly showed higher PCB levels than rural ones. Finally, calculation of TEQ equivalents of the coplanar PCBs in the sewage sludges revealed that, based on application rates normally used in Switzerland, the contribution of the sludges to soil pollution seems to be of minor importance.     

Long-Term Efficiency of Catalytic Converters Operating in Mexico City

ABSTRACT

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones.

The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NO_x emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure     

Long-term efficiency of catalytic converters operating in Mexico City

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones. The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NOx emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure FTP-75. Our results suggest that the replacement of old catalytic converters with new ones will have little effect on decreasing polluting emissions because these vehicles were in very bad mechanical condition. Results of catalytic activity as a function of mileage indicated inefficient catalyst performance for the fleets tested. All pollutant conversions were below 90% efficiency, and they deteriorated by an average of 30% after the vehicles were run for 100,000 km.     

Platinum and Palladium transfer to milk, organs and tissues after a single oral administration to lactating goats

Platinum (Pt) and Palladium (Pd) are massively used in catalytic converters, emitted with exhaust fumes and deposited on roadsides in particle sizes. If they are ingested by ruminants grazing in agricultural fields located along roads they may enter the food chain. The objective of this study is to assess the potential transfer of Pt (PtCl(2)) and Pd (PdCl(2)) towards milk, tissues (muscle) and organs (kidney, liver and mammary gland). Three lactating goats received orally a single dose of 200mg of Pd and 200mg of Pt at the beginning of the experiment. The milk was collected each day during eight days. On the eighth day, organs and tissues were sampled to analyse the metal concentrations by ICP-MS (quantification limit of 0.25ng/g for Pd and Pt, detection limit of 0.08ng/g). The experiment demonstrated a significant transfer of Pd and Pt to kidney. The detected concentration was, respectively, of 73.9ng/g DW and 268.5n/g DW (factor 22 and factor 73 compared to the control kidney). The amounts of metals were : in the liver,18.1ng/g DW for the Pd and 8.1ng/g DW for the Pt, in the mammary gland, 14.9ng/g DW fort the Pd and 2.5ng/g DW for the Pt and in the muscle, 4.9ng/g DW for the Pd and 0.6ng/g DW for the Pt. The Pd concentration detected in milk was higher (from 5ng/g DW to 9ng/g DW) than in control milk but the transfer factor remained very low (0.02%). The Pt in milk could not be detected because it was below the quantification limit (<0.25ng/g DW).     

Changes of polycyclic aromatic hydrocarbons during composting of sewage sludges with chosen physico-chemical properties and PAHs content

The aim of the experiment was to determine changes in the PAH content during sewage sludge composting. The extent was evaluated to which sewage sludge properties influences on PAHs losses during composting. Five municipal sewage sludges were studied from sewage treatment plants located in the south-east of Poland, i.e. in Stalowa Wola, Kra?nik, Lublin, Zamo?? and Bi?goraj. The treatment plants selected were characterised by their differentiation with catchments area as well as the industrial character of the areas. Sludge composting was carried out in aerobic conditions in plastic containers for a period of 76 days. The content of 14 polycyclic aromatic hydrocarbons (PAHs) and some physical-chemical (TOC, Nt, TOC/Nt, CEC, BS, TEB, pH, available potassium and phosphorus, total forms of cations) sewage sludge properties were monitored. In the present study correlations between PAHs losses (during various phases of composting) and physical-chemical properties of sewage sludges and composts were also evaluated. The sewage sludges were characterised both by differentiated properties and by PAH content. The total PAH content (the sum of 14 PAHs from the EPA List with exception of naphthalene and acenaphthene) in the sludges ranged from 3674 to 11236 microg kg(-1). Four- and three-ring compounds were predominant in the sewage sludges. Almost all of the sludges were characterised by differentiated content levels of both individual PAHs groups and PAHs sum. After 76 days of composting, a significant lowering of the PAH content was observed in all sludges as compared to the beginning of the experiment. The range of total observed PAH losses was from 15.8% to 48.6%, depending on the sewage sludge. The largest lowering of the PAH content was observed in the sludge with the lowest concentration of the xenobiotics studied. The largest losses in individual PAHs were observed in the case of five- and six-rings compounds, and were probably related to strong pollutant binding by other components of the sewage sludge. The few significant relationships showed that PAH losses during composting were only slightly determined by the analysed physical-chemical properties.     

Long-term study of palladium in road tunnel dust and sewage sludge ash

The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 μg Pd kg⁻¹ were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 μg Pd kg⁻¹ were found in the years 1986-1997. In both matrices correlations of Pd content to Pd demand of industry are discussed.     

Effects of past sewage sludge additions on heavy metal availability in light textured soils: implications for crop yields and metal uptakes

The effect of heavy metal additions in past sewage sludge applications on soil metal availability and the growth and yield of crops was evaluated at two sites in the UK. At Gleadthorpe, sewage sludges enriched with salts of zinc (Zn), copper (Cu) and nickel (Ni) had been applied to a loamy sand in 1982 and additionally naturally contaminated Zn and Cu sludge cakes in 1986. At Rosemaund, sewage sludges naturally contaminated with Zn, Cu, Ni and chromium (Cr) had been applied in 1968-1971 to a sandy loam. From 1994 to 1997, the yields of both cereals and legumes at Gleadthorpe were up to 3 t/ha lower than the no-sludge control where total topsoil Zn and Cu concentrations exceeded 200 and 120 mg/kg, respectively, but only when topsoil ammonium nitrate extractable metal levels also exceeded 40 mg/kg Zn and 0.9 mg/kg Cu. At Rosemaund, yields were only decreased where total topsoil Cu concentrations exceeded 220 mg/kg or 0.7 mg/kg ammonium nitrate extractable Cu. These results demonstrate the importance of measuring extractable as well as total heavy metal concentrations in topsoils when assessing likely effects on plant yields and metal uptakes, and setting soil quality criteria.     

Dioxin-like compounds in Australian sewage sludge--review and national survey

An Australian survey of dioxin-like compounds in sewage sludge was conducted in two parts (a) a national survey, and (b) a time-study. All sewage sludge samples analysed as part of these studies had low overall concentrations of dioxin-like compounds. Out of 37 samples, all except one, were within the reported concentration range of soil within the Australian environment. The mean concentration of dioxin-like compounds in the Australian sewage sludge survey of 2006 was found to be 5.6 (s.d. 4.5) ng WHO(05) TEQkg(-1) (n=14) and were within the range of 1.2-15.3 ng WHO(05) TEQ kg(-1). All the Australian sewage sludge samples cited in these studies were below the Victorian EPA "investigation limit" of 50 ng WHO(98) TEQ kg(-1), and well below the European proposed guidelines of 100 ng I-TEQ kg(-1). The burden of dioxin-like compounds in Australian sewage sludge is low and its land application as biosolids is not likely to pose a problem. A general positive relationship was found between population of the town producing the waste and both dioxin-like PCDD/Fs and dioxin-like PCBs. The one exception to this trend was sludge from a town that had a history of smelting and had a relatively high burden of dioxin-like compounds. Sludge from one rural WWTP also had a higher burden of dioxin-like compounds. The treatment plant services a geographically isolated town with a low population and no known emitters of dioxin-like compounds. However, this sample also had a relatively high burden of dioxin-like PCBs, which could be the source of the dioxin-like PCDD/Fs found in this sludge. The time study analyzing sludges from three WWTP from the same city between the years 2002 and 2006 found no apparent difference between WWTPs, but a statistically significant decline of 1.49 ng WHO(05) TEQ kg(-1) per year. Also, a comprehensive review of the scientific literature, presents typical levels and sources of dioxin-like compounds in international sewage sludges.     

Atmospheric deposition of polybrominated diphenyl ethers (PBDEs) in coastal areas in Korea

Atmospheric bulk samples were collected monthly, for one year, from urban, suburban, and rural sites located in the coastal areas of Korea, for the assessment of depositional fluxes and seasonal variations in atmospheric concentrations of PBDEs. Twenty individual PBDE congeners were found in atmospheric samples, and their depositional fluxes varied from 10.1 to 89.0 microg/m2/year. The highest depositional fluxes were found in two urbanized areas, with a strong urban-rural gradient. The relationship between PBDE and particulate depositional fluxes showed significant correlation for all locations, which suggested the association of PBDEs to particulate phase. Deca-BDE (BDE 209) was the predominant congener (>93%) in all deposition samples, which is consistent with a high consumption of deca-BDE for the flame-retardant market in Korea. Seasonal variability was observed in PBDE concentrations for the two urban sites, whereas no seasonal trend was found for either the suburban or the rural location.     

Long-term effect of sewage sludge application on soil humic acids

Sewage sludges are used in agriculture because they act as a fertilizer. Long-term studies are needed to evaluate the effect of sewage sludge on soil properties by paying particular attention to the soil organic matter. Soil plots were amended for 10 years with 1Mg dry matter ha(-1)year(-1) of sewage sludge. Chemical parameters such as total organic carbon (TOC), N, C/N ratio and CEC were determined when this period ended. Moreover, TOC was fractionated into humified and non-humified fractions. Humic acids (HA) were isolated and studied by elemental analysis, DRIFT, (1)H NMR and CPMAS 13C NMR spectroscopies. At the end of the tests, compared to the control soil, the sludge-amended soil did not exhibit change in total organic C and related humified fractions. However, the HA composition of the soil treated with sludge had developed an HA composition closer to that of the HA-sludge as a result of the enrichment of recalcitrant fractions contained in the sludge.