Characterization and environmental implications of nano- and larger TiO(2) particles in sewage sludge, and soils amended with sewage sludge

Titanium dioxide (TiO(2)) is the most extensively used engineered nanoparticle to date, yet its fate in the soil environment has been investigated only rarely and is poorly understood. In the present study, we conducted two field-scale investigations to better describe TiO(2) nano- and larger particles in their most likely route of entry into the environment, i.e., the application of biosolids to soils. We particularly concentrated on the particles in the nano-size regime due to their novel and commercially useful properties. First, we analyzed three sewage sludge products from the US EPA TNSSS sampling inventory for the occurrence, qualitative abundance, and nature of TiO(2) nano- and larger particles by using analytical scanning electron microscopy and analytical (scanning) transmission electron microscopy. Nano- and larger particles of TiO(2) were repeatedly identified across the sewage sludge types tested, providing strong evidence of their likely concentration in sewage sludge products. The TiO(2) particles identified were as small as 40 nm, and as large as 300 nm, having faceted shapes with the rutile crystal structure, and they typically formed small, loosely packed aggregates. Second, we examined surface soils in mesocosms that had been amended with Ag nanoparticle-spiked biosolids for the occurrence of TiO(2) particles. An aggregate of TiO(2) nanoparticles with the rutile structure was again identified, but this time TiO(2) nanoparticles were found to contain Ag on their surfaces. This suggests that TiO(2) nanoparticles from biosolids can interact with toxic trace metals that would then enter the environment as a soil amendment. Therefore, the long-term behavior of TiO(2) nano- and larger particles in sewage sludge materials as well as their impacts in the soil environment need to be carefully considered.     

Use of sequential extraction to assess the influence of sewage sludge amendment on metal mobility in Chilean soils

In Chile, the increasing number of plants for the treatment of wastewater has brought about an increase in the generation of sludge. One way of sludge disposal is its application on land; this, however involves some problems, some of them being heavy metal accumulation and the increase in organic matter and other components from sewage sludge which may change the distribution and mobility of heavy metals. The purpose of the present study was to determine the effect of sewage sludge application on the distribution of Cr, Ni, Cu, Zn and Pb in agricultural soils in Chile. Three different soils, two Mollisols and one Alfisol, were sampled from an agricultural area in Central Chile. The soils were treated with sewage sludge at the rates of 0 and 30 ton ha(-1), and were incubated at 25 degrees C for 45 days. Before and after incubation, the soils were sequentially extracted to obtain labile (exchangeable and sodium acetate-soluble), potentially labile (soluble in moderately reducing conditions, K4P2O7-soluble and soluble in reducing conditions) and inert (soluble in strong acid oxidizing conditions) fractions. A two-level factored design was used to assess the effect of sludge application rate, incubation time and their interaction on the mobility of the elements under study. Among the metals determined in the sludge, zinc has the highest concentration. However, with the exception of Ni, the total content of metals was lower than the recommended limit values in sewage sludge as stated by Chilean regulations. Although 23% of zinc in sludge was in more mobile forms, the residual fraction of all metals was the predominant form in soils and sludge. The content of zinc only was significantly increased in two of the soils by sewage sludge application. On the other hand, with the exception of copper, the metals were redistributed in the first four fractions of amended soils. The effect of sludge application rate, incubation time and their interaction depended on the metal or soil type. In most cases an increase in more mobile forms of metals in soils was observed as the final effect.     

Application of a modified BCR sequential extraction (three-step) procedure for the determination of extractable trace metal contents in a sewage sludge amended soil reference material (CRM 483), complemented by a three-year stability study of acetic acid and EDTA extractable metal content

This paper provides additional data on a sewage sludge amended soil certified reference material, CRM 483, which was certified in 1997 for its EDTA and acetic acid extractable contents of some trace metals, following standardised extraction procedures. The additional work aimed to test the long-term stability of the material and the applicability of an improved version of the BCR three-step sequential extraction procedure on the sewage sludge amended soil (CRM 483). The paper demonstrates the CRM 483 long-term stability for EDTA and acetic acid extractable contents of Cd, Cr, Cu, Ni, Pb and Zn and gives the results (obtained in the framework of an interlaboratory study) for the extractable contents of the same elements in the CRM 483, following the BCR three-step sequential extraction scheme. The aqua regia extractable contents following the ISO 11466 Standard are also given. The data are given as indicative (not certified) values.     

Assessment of aluminum bioavailability in alum sludge for agricultural utilization

Inorganic aluminum ions, [Al(H₂O)₆]³⁺, [Al(OH)(H₂O)₅]²⁺, and [Al(OH)₂(H₂O)₄]⁺, are toxic to a number of crops. The aim of this study was to estimate the danger of soil contamination of bioavailable aluminum and heavy metals forms because of alum sludge which was a by-product of water, and wastewater treatment technology using aluminum coagulant is introduced into the soil. Aluminum and selected heavy metal fractionation was carried out in the post-coagulation sludge collected at a water treatment plant (where aluminum was used as a coagulant), fermented sewage sludge at a municipal wastewater treatment plant (which did not apply aluminum coagulant), and soil from water treatment plant as well as the mixtures of sludge and soil. It has been found that post-coagulation sludge used as natural fertilizer is a secondary source of bioavailable aluminum, especially when aluminum coagulants are used during water and wastewater treatment. The evaluation of applicability of the sludge to very weak acidic and acidic agricultural soils was carried out. The authors shall debate the question whether, in this case, the Regulation of EU and Polish Government on sewage sludge should also take the bioavailable aluminum into account and add to the list of the elements whose allowable contents are limited.     

Nutrient transfer by runoff from sewage sludge amended soil under simulated rainfall

Wastewater sludges are used in agriculture as soil amendment and fertilizer, with regard to their organic matter and nutrient content. However, availability of nitrogen and phosphorus from sludge-amended soils and their transfer in runoff may lead to eutrophication of downstream surface water. The aim of this study is to establish and compare the effect of two different sludges on these transfers: an anaerobically digested and thermically stabilised sludge (Seine-Aval treatment plant, sludge no. 1), and a limed sludge (Saint-Quentin treatment plant, sludge no. 2). Experiments were performed on 12 sloping micro-plots (1 m × 1 m) submitted to sludge spreading and controlled rainfall simulation. Runoff water was sampled and analysed for concentrations in nitrogen species and phosphorus. Results show that spreading of sludge no. 1 increased both ammonium nitrogen (mean of 1.1 mg L^–1 N-NH₄ vs. 0.2 mg L^–1 N-NH₄ for control micro-plots) and particulate phosphorus concentrations (mean of 2 mg L^–1 P vs. 1.1 mg L^–1 P for control micro-plots) in runoff water. On the other hand, sludge no. 2 did not induce any significant effect on nutrient concentrations in runoff. These results are related to chemical composition and physical treatment of sludges. This study underlines the existence of a short-term risk of nutrient mobilisation by runoff after sludge spreading on soil, and the need to check precisely the impact of this practice on water quality.     

Comparison of TCPP concentrations in sludge and wastewater in a typical German sewage treatment plant-comparison of sewage sludge from 20 plants

Tris(chloro-isopropyl)phosphate (TCPP) was identified by GC-MS by comparing mass spectra and retention times to original standards. The concentrations in wastewater of a sewage treatment plant's influent and effluent were analysed (520 ng l(-1) and 380 ng l(-1), respectively (mean values). The concentrations of TCPP in the wastewater inflow exhibited a high variability. The elimination of this compound in the sewage treatment plant also exhibits a high variability but is low. Additionally the concentrations in sewage sludge of the same plant were determined (mean value 5100 ng g(-1) dry weight; 1700 ng g(-1) wet weight, respectively). For a comparison sludge samples from twenty other plants were analysed. In these samples concentrations ranging from 1000-20000 ng g(-1)(dry weight) were determined. Thus sorption to sludge does occur to some extent.     

Phthalate and alkyl phenol concentrations in soil following applications of inorganic fertiliser or sewage sludge to pasture and potential rates of ingestion by grazing ruminants

Soil concentrations of dioctyl phthalate (DOP) and the alkyl phenols, octyl phenol (OP) and nonyl phenol (NP), after repeated surface applications of sewage sludge to pastures, were investigated. Liquid sludge was applied at a rate of 2.25 tonnes dry matter (DM) per hectare to each of three treated (T) plots on three occasions during the summer and two occasions in the early spring over a period of 2.5 years. Control (C) plots were treated with inorganic fertiliser containing amounts of nitrogen equivalent to those applied to the treated plots. At between 69 and 81 days after the application of sludge, 15 separate soil samples were collected from one half of each of the plots (Experiment 1). Concentrations (microg g(-1)) of DOP were higher (P < 0.001) than those of NP, while those of OP were generally below detectable levels. Mean soil concentrations of DOP were not significantly different in T and C plots [0.233 vs. 0.155 microg g(-1); standard error of the difference (SED) = 0.046; not significant (NS)], partly because there was already a relatively large amount of DOP present. NP concentrations were, however, significantly higher in T than in C plots (0.021 vs. 0.013 microg g(-1) SED = 0.002; P < 0.05). There was no consistent change over time in the mean soil concentrations of these compounds when sampled at intervals of 3-6 months. Concentrations in soil samples collected at monthly intervals following sludge application indicated that the variation in concentrations of these endocrine-disrupting compounds (EDC) was unrelated to time since sludge application. Rates of soil ingestion, expressed as the percentage of DM intake represented by soil, were higher during the winter than the summer (5.40 vs. 1.17; SED = 0.360; P < 0.001) and estimated daily intakes of DOP and NP were up to 150 microg and 8 microg, respectively. It is concluded that the application of sewage sludge to pasture does not increase soil concentrations of phthalate (as DOP) or alkyl phenols. Thus, the risk of increased exposure to these EDC as a result of sludge application is small. However, the small effect of sludge application on soil concentrations may be largely a reflection of the relatively high concentrations of DOP already present in the soil, which may be biologically significant.     

Direct electrothermal atomic spectrometric determination of Ag in aqua regia extracts of soils, sediments, and sewage sludge with matrix modification

Silver is subject to significant interferences caused by high chloride concentrations in electrothermal atomic absorption spectrometry, thus its direct determination in aqua regia leaches from soils, sediments, and sludges is very difficult, especially when using instrumentation equipped with deuterium-lamp background correction (D₂). In this study, the interference of the aqua regia medium was successfully eliminated using Pd–citric acid chemical modifier. This chemical modifier was found to be the most advantageous in comparison with Pd mixture with ascorbic acid, tartaric acid, or citric acid–Li based on its ability to suppress the interference originating from different chloride matrix. Palladium increases the analyte stability; citric acid serves as a reducing reagent, and furthermore, it helps to remove the interfering chlorides by forming HCl, in the drying step of the electrothermal program. In the presence of the modifier, the pyrolysis temperature can be adjusted up to 1,000 °C with no loss of the analyte. The obtained limit of detection and characteristic mass were 5 ng g^?1 and 1.7 pg, respectively. The accuracy of the method was verified by means of six different reference samples and by comparing the results of the analysis of real samples with those obtained by inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometer. The proposed method was applied to the Ag determination in soils, sediments, and sewage sludge samples from the Pardubice region in Czech Republic.     

Influence of sewage sludge,as a substrate,in the plasticity of functional characteristics of plants

This work aimed to evaluate the effect of sewage sludge application as fertilizer on the plasticity of functional characteristics of species commonly found in the Caatinga. The research was developed in the nursery of the Federal Institute of Education, Science and Technology of Ceará (IFCE), Quixadá campus, located in northeastern Brazil. Three treatments were applied: raw sludge, sanitized sludge, and no manipulation. In each treatment, five species were planted, each with five individuals, totaling 75 individuals, which were tagged, and 4 months after germination, they were destroyed to obtain dry matter content (TMSF) from leaf, stem (TMSC), fine root (TMSRF), and thick root (TMSRG); leaf area; height and diameter of the seedling; and length above and below the ground. The sanitized sludge was responsible for giving higher values for leaf area, height of the seedlings, and diameter and length of stem and root. However, the dry matter content of the fine roots was higher in the treatment without manipulation. At the community level, as TMSRG increased, TMSC also increased, the same occurred between TMSRG and TMSRF, TMSC and TMSRF, and stem length and leaf area. In the treatment without manipulation, there was a positive correlation between leaf area, height and plant diameter, and negative correlation between root length and plant diameter. Thus, it can be concluded that the use of sanitized sludge is a good tool to increase the availability of soil resources, conferring to individuals’ greater dry matter content, greater leaf area, and higher height and diameter above the ground.     

Chemical, biochemical, and biological impact of untreated domestic sewage water use on Vertisol and its consequences on wheat (Triticum aestivum) productivity

In the peri-urban areas of central India, sewage water is a valuable resource for agricultural production. In this study, impact of domestic sewage water irrigation for 5 years on Vertisol with no previous history of sewage irrigation was investigated in an ongoing field experiment at Bhopal (India) under subtropical monsoon type climate. The wheat (Triticum aestivum) crop was grown during post-rainy winter season with 30 cm of irrigation (groundwater or sewage water) and four nutrient treatments (T₁, 0; T₂, 100%; T₃, 50%; and T₄, 50% of general recommended doses of NPK + FYM at 10 Mg/ha). Results showed that sewage irrigation of about 150 cm over a period of 5 years resulted significant increases in salinity as well as available fractions of N, P, K, and micronutrients, viz., Zn, Fe, and Mn in soils. Carbon and phosphorus applied through sewage water were accumulated more in subsoil layer compared to topmost plough layer. Soil microbiological activity, as indicated by soil respiration, microbial biomass C, as well as dehydrogenase enzyme activity was higher in sewage water-irrigated soils. There was also significant increase in fungal and actinomycetes as well as total coliform population in such soils. Nutrients supplied through sewage water were not able to raise the productivity of wheat to the level that obtained through fertilizers at the recommended level which indicated that additional nutrients through fertilizers are required to obtain higher productivity of wheat under sewage farming. Protein and Zn content in wheat grains were more when the crop was grown with sewage irrigation. Overall results show that except for increase in coliform population, short duration (5 years) of municipal sewage water irrigation did not have any appreciable harmful effect on soil quality as well as crop productivity; rather, it proved beneficial in improving soil fertility, wheat productivity, and produce quality.     

Monitoring of toxic elements present in sludge of industrial waste using CF-LIBS

Industrial waste is one of the main causes of environmental pollution. Laser-induced breakdown spectroscopy (LIBS) was applied to detect the toxic metals in the sludge of industrial waste water. Sludge on filter paper was obtained after filtering the collected waste water samples from different sections of a water treatment plant situated in an industrial area of Kanpur City. The LIBS spectra of the sludge samples were recorded in the spectral range of 200 to 500 nm by focusing the laser light on sludge. Calibration-free laser-induced breakdown spectroscopy (CF-LIBS) technique was used for the quantitative measurement of toxic elements such as Cr and Pb present in the sample. We also used the traditional calibration curve approach to quantify these elements. The results obtained from CF-LIBS are in good agreement with the results from the calibration curve approach. Thus, our results demonstrate that CF-LIBS is an appropriate technique for quantitative analysis where reference/standard samples are not available to make the calibration curve. The results of the present experiment are alarming to the people living nearby areas of industrial activities, as the concentrations of toxic elements are quite high compared to the admissible limits of these substances.     

Effects of treated sewage sludge levels on temporal variations of some soil properties of a Typic Xerofluvent soil in Menemen Plain, Western Anatolia, Turkey

The aim of this study is to determine effects of treated sewage sludge (TSS) levels as an organic matter (OM) resource on temporal variations of some soil properties of a Typic Xerofluvent soil. The experiment was conducted in Menemen Plain, in the Western Anatolia Region of Turkey (latitudes 38 degrees 34'48.22'-38 degrees 34'49.24' N; longitudes 27 degrees 1'23.05-27 degrees 1'24.14' E) in the years of 2003 and 2004. Moist TSS was added to the soil at the rates of 0, 30, 60 and 90 t ha(-1) on May 1, 2003. Peanut (Arachis hypogaea) was planted as first crop. On the other hand, mixture of green barley (Hordeum vulgare) and common vetch (Vicia sativa L.) was planted as second crop. During the experiment, soil samples were taken in five different periods (1st, June 18, 2003; 2nd, November 13, 2003; 3rd, April 30, 2004; 4th, October 10, 2004 and 5th, May 12, 2004). The results showed that increasing TSS application to Typic Xerofluvent soil was significantly increased total salt, OM, total porosity, micro porosity, macro porosity, field capacity, wilting point, available water content, structure stability index and aggregation percentage values of soil when compared with control. Meanwhile, particle density, dry bulk density and nonaggregated silt + clay values of soil decreased. On the other hand, soil reaction (pH), lime content and total silt + clay values of soil did not significantly change. In the course of time, depending on decomposing of TSS organic materials in soil, effect of TSS levels on soil properties decreased particularly in the last periods. For this reason, it can be recommended that 90 t ha(-1) moist TSS can be added once in 2 years for improving soil properties of Typic Xerofluvent soil, which are characterized by low OM content.     

Sediments as a potential tool for assessment of sewage pollution in Barigüi River, Brazil

Sediments constitute a pollutant trap and have proven to be an efficient tool to identify environmental impacts. Sediments are considered a very important means to assess the level of contamination of water bodies because of their ability to accumulate metals and organic. The anthropogenic inputs of sewage, with or without prior treatment, in aquatic environments, affect the geochemical composition of sediment. In addition, the sediment adsorbs hydrophobic compounds found in feces, such as the fecal sterols. The granulometric and geochemical composition of the sediment of Barigüi River-Brazil was investigated. The results show that silt and clay dominate the granulometric composition of the sediments. The geochemical composition of sediments showed high concentrations of phosphorus and nitrogen. The Redfield ratios confirm the inputs of phosphorus and nitrogen. The TOC/N ratio was used to identify the source of pollution. N/TP ratios were found between 1.0 and 3.5. Clearly, an input of phosphorus, sewage is the most acceptable source, following the historic profile of the Barigüi River. High concentration of nitrogen phosphorus labels the area to be polluted by sewage. To confirm the sewage pollution, adsorbed fecal sterols in sediments were investigated. The concentration of total sterols was found between 0.86 and 304.58 μg g^???1. Two distinguished scenario was found, one severely polluted and another slightly polluted. The highest concentrations of total fecal sterols were associated with sediment whose geochemical composition showed higher levels of TOC, as well as higher proportions of silt and clay. Also, epicoprostanol, a coprostanol isomer, was used as an indicator of the level of treatment or age of the fecal matter because it is formed during the treatment of wastewater and sludge digestion. If the treatment of sludge takes a long time, epicoprostanol can form from cholesterol, and relative proportions of those compounds may be used as an indicator of the presence of untreated sewage in the sediments. The epicoprostanol was found in the range between 0.02 and 9.71 μg g^???1; concentration of up to 0.015 μg g^???1 represents situations where there is strong contamination by sewage. All sites investigated showed a concentration of epicoprostanol higher than the value adopted as threshold. The lower concentration of epicoprostanol found for all sites is consistent with the high concentration found for coprostanol, and this is typical for untreated sewage.     

Accumulation of heavy metals in Spinacia oleracea irrigated with paper mill effluent and sewage

The present study on heavy metal contamination in soil and their accumulation in edible part (leaves) and roots of Spinacia oleracea (Spinach) on irrigation with paper mill effluent (PME)/sewage revealed that there was significant increase in the nickel (Ni, +227.17 %) content of the soil irrigated with PME, whereas in the soil irrigated with sewage chromium (Cr, +274.84 %), iron (Fe, +149.56 %), and cadmium (Cd, +133.39 %), contents were increased appreciably. The value of enrichment factor (EF) for Ni (3.27) indicated moderate enrichment in PME-irrigated soil. The EF of Fe, zinc (Zn), Cd, and Cr were <2 in PME effluent-irrigated soil which showed deficiency of minimal enrichment. In sewage irrigated soil, EF value for Cr, Fe, and Cd indicated moderate enrichment, while the values for Zn and Ni indicated deficiency of minimal enrichment. Among various metallic concentrations, the maximum concentration of Fe was observed in leaves (400.12?±?11.47 mg/kg) and root (301.41?±?13.14 mg/kg) of S. oleracea after irrigation with PME, whereas the maximum concentrations of Fe was found in leaves (400.49?±?5.97 mg/kg) and root (363.94?±?11.37 mg/kg) of S. oleracea after irrigation with sewage for 60 days. The bioaccumulation factor value was found maximum for Cd (2.23) in the plants irrigated with PME while that of Fe (0.90) in the plants irrigated with sewage. The undiluted use of PME/sewage for irrigation increased the concentration of Cr, Cd, Zn, Ni, and Fe metals which were accumulated in S. oleracea, posing a potential threat to human health from this practice of irrigation.     

Organic contaminants in the Firth of Clyde following the cessation of sewage sludge dumping

To assess contaminant concentrations in the Firth of Clyde in relation to the former sewage sludge dump site at Garroch Head, and investigate any temporal changes, fish have been sampled annually since 1992 and sediment since 1999. In addition, a further four locations in the Clyde (Holy Loch, Hunterston, Skelmorlie and Irvine Bay) have been sampled for fish and sediment since 1999. Chlorobiphenyls (CBs) were measured in fish samples and polycyclic aromatic hydrocarbons (PAHs) and CBs in sediment. Since sampling was initiated the concentration for the summation operatorICES7 CBs in fish liver has been consistently >500 microg kg(-1) lipid weight at Garroch Head and the other Clyde sites and lower at the reference sites (Pladda, Colonsay, Broad Bay). Although the lowest CB concentrations of the eleven year period in plaice liver from Garroch Head were found in 2002, CB concentrations were found not to have decreased significantly since sewage sludge dumping ceased in 1998. However, a change in CB profile was observed with fish liver collected between 1992 and 1998 from Garroch Head showing a lower proportion of the less chlorinated CBs compared to the 1999-2002 liver samples. Highest CB and PAH concentrations in sediment were found at Garroch Head and Holy Loch with concentrations at these sites being significantly higher than at all other sites.     

Natural attenuation of coal combustion waste in river sediments

The weathering of coal combustion products (CCPs) in a lotic environment was assessed following the Tennessee Valley Authority (Kingston, TN) fly ash release of 2008 into surrounding rivers. Sampled materials included stockpiled ash and sediment collected from 180 to 880 days following the release. Total recoverable concentrations of heavy metals and metalloids in sediment were measured, and percent ash was estimated visually or quantified by particle counts. Arsenic and selenium in sediment were positively correlated with percent ash. For samples collected 180 days after the release, total concentrations of trace elements downstream of the release were greater than reference levels but less than concentrations measured in stockpiled ash. Total concentrations of trace elements remained elevated in ash-laden sediment after almost 2.5 years. A sequential extraction procedure (SEP) was used to speciate selected fractions of arsenic, copper, lead, nickel, and selenium in decreasing order of bioavailability. Concentrations of trace elements in sequentially extracted fractions were one to two orders of magnitude lower than total recoverable trace elements. The bulk of sequentially extractable trace elements was associated with iron-manganese oxides, the least bioavailable fraction of those measured. By 780 days, trace element concentrations in the SEP fractions approached reference concentrations in the more bioavailable water soluble, ion exchangeable, and carbonate-bound fractions. For each trace element, the percentage composition of the bioavailable fractions relative to the total concentration was calculated. These SEP indices were summed and shown to significantly decrease over time. These results document the natural attenuation of leachable trace elements in CCPs in river sediment as a result of the loss of bioavailable trace elements over time.     

Investigation into antimony mobility in sewage sludge fermentation

Antimony is distributed in the environment in inorganic and organic species with different solubility and mobility characters. Here we investigate the transformation of antimony in view of biomethylation during sewage sludge fermentation as a case study for an anaerobic environment. Our approach was to identify if antimony methylation follows the Challenger pathway by using isotopically enriched antimonite (123Sb(v)). The antimony source was subjected to methylation in sewage sludge, an anaerobic dominant methanogenic Archaea community. The antimony species were determined in the gas phase using cryotrapping (CT)-GC-ICP-MS, and in the medium (sewage slude) by hydride generation (HG) prior CT-GC-ICP-MS. The determined 123/121Sb isotope ratios in the volatile trimethylstibine and non-volatile methylantimony species indicated that the methylation follows the proposed methylation pathway. With this approach we were able to quantify 123Sb incorporation into monomethyl-, dimethyl- and trimethylantimony, respectively. The incorporation decreased with further methylation from 91% to 82% and 73%. Volatilisation as trimethystibine was generally lower than 0.1%, however, up to 0.8% of added antimony was found methylated to methylantimony species and mainly accumulated in the cell. Moreover, antimony biomethylation was enhanced by stimulation of the anaerobic communities of methanogenic Archaea and sulfate reducing bacteria (SRB), with the methanogens showing a higher activity.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Identification of surfactant degradation products as toxic organic compounds present in sewage sludge

A cost-effective strategy combining chemical analysis and bioassays for the identification of polar toxic compounds in sewage sludge is reported. ToxAlert 100 bioluminescence inhibition assay was used in combination with chemical analysis involving extraction, clean-up, chromatographic separation and mass spectrometry detection. This methodology was applied to real samples of sludge from three wastewater treatment plants (WWTP) located in Catalonia (Spain) during a 3 month period. In the first step, sewage sludge was lyophilized, treated by sonication with a mixture of methanol and chloroform and finally cleaned up using a sequential solid phase extraction (SSPE) with an octadecylsilica cartridge (C18) in series with a polymeric Lichrolut EN cartridge (Lic EN). In the second step, the toxicity of each fraction of the sludge sample was investigated using the ToxAlert 100. The unequivocal identification and quantification of polar organic cytotoxic substances present in the fractionated extracts were determined by liquid chromatography-mass spectrometry (LC-MS). Major toxic compounds identified were: non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their intermediates (polyethylene glycol polyethoxylated, nonylphenol carboxylates and polyethoxylated alcohol carboxylates), linear alkylbenzenesulfonates and heavy metals. The toxic response (in terms of bioluminescence inhibition using ToxAlert 100), defined by the 50% effective concentration (EC50), and the toxicity units (TU) for every standard non-ionic surfactant were calculated. The results provided the identification of polar cytotoxic compounds as well as the evaluation of their contribution to the total toxicity observed in sewage sludge.     

Heavy metals in Yeniçağa Lake and its potential sources: soil,water, sediment,and plankton

The distribution and accumulation of heavy metals (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sn, Ba, Pb) in the water, sediments, plankton of Yeniça?a Lake, and its potential sources (creeks, sewage, artesian well, soil) were investigated during 1-year study period as monthly or seasonally. Element analyses were performed by ICP–MS. Results showed that the trace and toxic elements (Al, As, Mn, Pb, Fe) concentration in lake water and/or its feeding sources were above the recommended water standards (WHO, EC, EPA, TS-266). It was found that the maximum accumulation of the heavy metals iron, aluminum, manganese, zinc, and barium in the sediment of Yeniça?a Lake. The accumulation order of trace metals were Fe > Al > Mn > Zn > Ba > Ni > Cr > As > Cu > Pb > Co > Mo > Sn > Cd in the lake, creeks sediment, and soil samples. The similar results suggest that the accumulation of heavy metals in the sediment is a natural process. Metals accumulated in the lake are naturally mixed from the soil. However, the presence of heavy metals in the analysis of artesian well water and sewage reveals that the transportation occurs also from the groundwater to the lake. The results obtained in plankton in Yeniça?a Lake showed that aluminum, iron, manganese, zinc, and barium were most accumulated elements in the plankton. The lower averages of lead prevalent in the water and sediment during some months were seen to have a significant mean accumulation in the plankton.