Method development and implementation for co-planar polychlorinated biphenyls (PCBs)

The Emission Measurement Center (EMC) in the Environmental Protection Agency's Office of Air Quality Planning and Standards was directed to conduct an emissions test program at a sewage sludge incinerator in support of a Maximum Achievable Control Technology (MACT) standard. One pollutant category of concern at these facilities was polychlorinated biphenyls, or PCBs. An objective of the test program was to measure co-planar PCBs in the incinerator emissions, the sewage sludge introduced to the incinerator, and the scrubber water effluent used in controlling the incinerator emissions. Co-planar PCB congeners are those having four or more chlorine atoms with only a few substitutions in the ortho positions, i.e. positions designated 2, 2', 6, and 6'. Thirteen PCB compounds are sometimes referred to as the "WHO PCBs," because the World Health Organization (WHO) has derived toxic equivalency factors for these congeners. Studies have shown that these dioxin-like compounds can react with the aryl hydrocarbon receptor. This same reaction is believed to initiate adverse health effects for dioxin and furan congeners. In order to conduct the co-planer PCB testing, the EMC had to develop analytical methods that could measure the 13 co-planar PCBs. The purpose of the test program was to develop, evaluate, and implement analytical test methods capable of measuring co-planar PCBs in three matrices: incinerator stack gases, sewage sludge, and scrubber water effluents. The paper summarizes the initial development work that was performed in preparation of analytical test protocols that could measure co-planar PCBs in air, water, and sludge matrices. Following the method development, a MACT emissions test program was conducted at a sewage sludge facility in July 1999 and these data are also summarized in the paper.     

Effect of compost treatment of sewage sludge on nitrogen behavior in two soils

This work aims to evaluate the effects of compost treatment of digested sewage sludge on nitrogen behavior in two soils, a Spodosol and an Oxisol soil. Digested sewage sludge was composted with sawdust and woodchips, diluting the total nitrogen to one-fourth (dry mass basis) of its original value. Then, sludge and compost were added to the two soils on an equivalent dry weight basis to consider the risk of NO3- -N leaching. Compost treatment of sewage sludge has slowed down the release of mineral-N to half in the Spodosol and to one-third in Oxisol soil. As a result, NO3- -N concentrations in soils incubated with compost were less than half of the amounts found from soils incubated with digested sludge. Estimates were made of the maximum monthly nitrate to leach from the four combinations of soil and sludge treatment. Application of digested sludge, at a higher nitrogen application rate, resulted in a higher nitrate leaching potential than application of the compost product. Soil type also played an important role, with the Oxisol having slightly higher estimated leaching potential than the Spodosol. The higher nitrate release rate in the Oxisol is counterbalanced by its higher field capacity to lessen the expected difference between the two soils.     

Waste paper and clinoptilolite as a bulking material with dewatered anaerobically stabilized primary sewage sludge (DASPSS) for compost production

Environmental problems associated with sewage sludge disposal have prompted strict legislative actions over the past few years. At the same time, the upgrading and expansion of wastewater treatment plants have greatly increased the volume of sludge generated. The major limitation of land application of sewage sludge compost is the potential for high heavy metal content in relation to the metal content of the original sludge. Composting of sewage sludge with natural zeolite (clinoptilolite) can enhance its quality and suitability for agricultural use. However, the dewatered anaerobically stabilized primary sewage sludge (DASPSS) contained a low concentration of humic substances (almost 2%), and the addition of the waste paper was necessary in order to produce a good soil conditioner with high concentrations of humics. The final results showed that the compost produced from DASPSS and 40-50% w/w of waste paper was a good soil fertilizer. Finally, in order to estimate the metal leachability of the final compost product, the generalized acid neutralization Capacity (GANC) procedure was used, and it was found that by increasing the leachate pH, the heavy metal concentration decreased. The application of the sequential chemical extraction indicated that metals were bound to the residual fraction characterized as a stabilize fractions.     

Use of thermal analysis techniques (TG-DSC) for the characterization of diverse organic municipal waste streams to predict biological stability prior to land application

The use of organic municipal wastes as soil amendments is an increasing practice that can divert significant amounts of waste from landfill, and provides a potential source of nutrients and organic matter to ameliorate degraded soils. Due to the high heterogeneity of organic municipal waste streams, it is difficult to rapidly and cost-effectively establish their suitability as soil amendments using a single method. Thermal analysis has been proposed as an evolving technique to assess the stability and composition of the organic matter present in these wastes. In this study, three different organic municipal waste streams (i.e., a municipal waste compost (MC), a composted sewage sludge (CS) and a thermally dried sewage sludge (TS)) were characterized using conventional and thermal methods. The conventional methods used to test organic matter stability included laboratory incubation with measurement of respired C, and spectroscopic methods to characterize chemical composition. Carbon mineralization was measured during a 90-day incubation, and samples before and after incubation were analyzed by chemical (elemental analysis) and spectroscopic (infrared and nuclear magnetic resonance) methods. Results were compared with those obtained by thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Total amounts of CO₂ respired indicated that the organic matter in the TS was the least stable, while that in the CS was the most stable. This was confirmed by changes detected with the spectroscopic methods in the composition of the organic wastes due to C mineralization. Differences were especially pronounced for TS, which showed a remarkable loss of aliphatic and proteinaceous compounds during the incubation process. TG, and especially DSC analysis, clearly reflected these differences between the three organic wastes before and after the incubation. Furthermore, the calculated energy density, which represents the energy available per unit of organic matter, showed a strong correlation with cumulative respiration. Results obtained support the hypothesis of a potential link between the thermal and biological stability of the studied organic materials, and consequently the ability of thermal analysis to characterize the maturity of municipal organic wastes and composts.     

The toxicity of composts from sewage sludges evaluated by the direct contact tests phytotoxkit and ostracodtoxkit

Limitations relating to permissible standards of undesirable substances in sewage sludges make it necessary to optimize sludge properties. One of the methods to achieve the above goal is the use of a composting process. The aim of this study was to determine the toxicity of composts obtained from sewage sludges composted for 76 days. Dewatered sewage sludges were collected from the four wastewater treatment plants located in the south-eastern part of Poland (Kraśnik, Lublin, Biłgoraj and Zamość). The sludges were mixed with standard OECD soil at doses of 6% and 24%. Phytotoxkit (with Lepidium sativum) and ostracodtoxkit (with Heterocypris incongruens) tests were used to evaluate toxicity. The results obtained showed different toxicity of sewage sludge depending on the sludge dose and bioassay used. H. incongruens mortality ranged from 0% to 90% and depended on the sewage sludge. The greatest inhibition of test organism growth was noted at a level of 55%. In the case of the Phytotoxkit test, a clearly negative influence of the sewage sludges on seed germination was observed at a dose of 24%. Root growth inhibition was noted in the case of most sewage sludges and was at a level of 20–100%. The influence of the composting on the toxicity of biosolids also showed various trends depending on the sludge type. Sludge composting often resulted in a toxicity increase in relation to H. incongruens. In the case of plants (Phytotoxkit test) and most sewage sludges, however, the composting process influenced both the seed germination and root growth in a positive way.     

Evaluation of an organic soil amendment generated from municipal solid waste seeded with activated sewage sludge

This study investigated the feasibility of using fresh activated sewage sludge as inoculum for the microbial valorization of segregated municipal solid waste and evaluated the quality of organic soil amendment generated. Organic fraction of municipal solid waste, which consisted of vegetative (vegetable, fruit and flower) wastes was seeded with activated sewage sludge and processed by rapid aerobic microbial treatment. Efficacy of microbial valorization process and quality of final product were assessed by physico-chemical analysis. Suitability of final product was assessed with regard to heavy metal content, pesticide residues, microbiological quality and phytotoxicity. Quality of the soil amendment generated was compared with the control product generated with a commercial microbial inoculum. Phytotoxicity experiments indicated the stimulatory effect of sewage sludge seeded soil amendment on plant growth but inhibition was observed in closed growth test due to the evolution of gaseous phytotoxic agents. The study suggests that segregated municipal solid waste can be effectively valorized with activated non-dewatered sewage sludge as inoculum and the quality of soil amendment generated was comparable to compost intended for unrestricted applications.     

Changes in soil chemical and microbiological properties during 4 years of application of various organic residues

A 4-year field trial was established in eastern Sweden to evaluate the effects of organic waste on soil chemical and microbiological variables. A simple crop rotation with barley and oats was treated with either compost from household waste, biogas residue from household waste, anaerobically treated sewage sludge, pig manure, cow manure or mineral fertilizer. All fertilizers were amended in rates corresponding to 100kgNha(-1)year(-1). The effects of the different types of organic waste were evaluated by subjecting soil samples, taken each autumn 4 weeks after harvest, to an extensive set of soil chemical (pH, Org-C, Tot-N, Tot-P, Tot-S, P-AL, P-Olsen, K-AL, and some metals) and microbiological (B-resp, SIR, microSIR active and dormant microorganisms, PDA, microPDA, PAO, Alk-P and N-min) analyses. Results show that compost increased pH, and that compost as well as sewage sludge increased plant available phosphorus; however, the chemical analysis showed few clear trends over the 4 years and few clear relations to plant yield or soil quality. Biogas residues increased substrate induced respiration (SIR) and, compared to the untreated control amendment of biogas residues as well as compost, led to a higher proportion of active microorganisms. In addition, biogas residues increased potential ammonia oxidation rate (PAO), nitrogen mineralization capacity (N-min) as well as the specific growth rate constant of denitrifiers (microPDA). Despite rather large concentrations of heavy metals in some of the waste products, no negative effects could be seen on either chemical or microbiological soil properties. Changes in soil microbial properties appeared to occur more rapidly than most chemical properties. This suggests that soil microbial processes can function as more sensitive indicators of short-term changes in soil properties due to amendment of organic wastes.     

Effect of composted sewage sludge application to soil on sweet pepper crop (Capsicum annuum var. annuum) grown under two exploitation regimes

The aim of this study is to monitor the effect of the application of three increasing amounts of composted sewage sludge (3, 6 and 9 kg compost m(-2)) on the physico-chemical properties of a horticultural calcareous soil where sweet pepper plants (Capsicum annuum var. annuum) cv. California were grown. A comparative study of two different exploitation regimes was carried out; the first was an open-air field-grown plot and the second plot was kept under controlled conditions in a greenhouse. Changes in physical and chemical properties measured in soil and sweet pepper crop were recorded during crop growth in order to measure the evolution of these properties as a consequence of increasing compost applications. Organic matter, total nitrogen Kjeldahl and available phosphorus contents increased in soil after composted sewage sludge applications. The 9 kg compost m(-2) application promoted the appearance of deleterious effects on the properties of soil, such as salt accumulation, a significant increase in the electrical conductivity and an input of heavy metals (Pb>Cr>Cd). The 6 kg compost m(-2) application provided a supply of nutrients necessary to grow peppers plants under both exploitation regimes. Pepper fruit biomass production under greenhouse was almost 60% higher compared to that of the open-air plot. Lower contents of Ca and increased levels of Cu in fruit under greenhouse growing conditions compared to those of open-air grown peppers seemed to promote the occurrence of blossom-end rot, affecting more than 10% of the harvested fruits.     

Bacterial community patterns and thermal analyses of composts of various origins.

During composting, the degradation of organic waste is accompanied and driven by a succession of microbial populations exhibiting a broad range of functional capabilities. Detailed inventories of the microbial communities in mature compost, however, are not available. Mature composts, originating from biowaste as well as sewage sludge and anaerobic sludge, were studied by denaturing gradient gel electrophoresis-fingerprints after polymerase chain reaction (PCR) amplification of the 16S rRNA genes using three different universal primer pairs, as well as by differential scanning calorimetry and thermogravimetry. The composts of different origin had different bacterial communities. The influence of different 16S rDNA primer sets on the same batches of compost DNA was evaluated. The clearest separation of different compost types was obtained by using the PCR primer pair 338f + 518r which is suggested for future applications. Communities from the different biowaste compost samples clustered together and could be separated from sewage sludge communities indicating the establishment of different microbial consortia. A similar differentiation of composts was found with the thermogavimetric analyses. It may thus be concluded that the resulting humus quality is closely linked to the microbial communities involved.     

Assessment of compost quality for its environmentally safe use by means of an ecotoxicological test on a soil organism

A research project was carried out to evaluate toxicological effects of compost addition to agricultural soil using the earthworm Eisenia foetida (Annellida) as a representative organism of the soil fauna. Moreover, the correlation between compost biochemical stabilization and toxicity at different phases of the composting process was assessed. Samples were collected from three composting plants at three different maturation levels (beginning of the composting process, intermediate compost after bio-oxidation, and mature refined compost). Two tests were performed: a standard chronic solid-phase test and an acute solid-phase test (developed originally by the authors). In the first test, the measured end-points were mortality, growth and reproduction; while in the second test earthworms’ behavior was evaluated. The chosen compost concentrations in soil ranged from 2.5 to 100 %, with the aim of obtaining the toxicological parameters (LC50) and to mimic real agricultural dosages for the lower concentrations. Results indicated an increase in compost toxicity with greater compost concentrations; in particular, agricultural compost dosage below 10 % showed no toxicity. Moreover, toxicity did not decrease during composting; intermediate compost showed the highest LC50 values. As a consequence, no correlation was ascertained between the results of ecotoxicological analysis and waste biochemical stability parameters during the composting process.     

Limitation of the concentration of organic pollutants in sewage sludge for agricultural purposes: A case study in South Spain

In 2000, the EU published the third draft of a future sludge directive entitled “Working document on sludge” where limit values for some organic compounds, including di-(2-ethyhexyl)phthalate (DEHP), sum of nonylphenol (NP), nonyphenol mono-(NP1EO) and diethoxylates (NP2EO), seven polychlorinated biphenyl congeners (PCB), polycyclic aromatic hydrocarbons (PAH) and linear alkylbenzene sulphonates (LAS), are fixed. In the present work, the monitoring of these organic compounds in sludge samples from four wastewater treatment plants (WWTPs) is reported. All WWTPs use anaerobic biological stabilization of sludge. The highest concentration levels were found for LAS, NPE and DEHP, in this order, with, in general, anaerobically-digested dehydrated sludge and compost samples being the most contaminated samples. DEHP, NPE, LAS and PAH were found at concentration levels above the limit values fixed in the third draft of the future EU sludge directive in the 44%, 88%, 13% and 6% of the analyzed anaerobically-digested dehydrated sludge and compost samples.     

Ecotoxicological assessment and evaluation of a pine bark biosorbent treatment of five landfill leachates

When selecting a landfill leachate treatment method the contaminant composition of the leachate should be considered in order to obtain the most cost-effective treatment option. In this study the filter material pine bark was evaluated as a treatment for five landfill leachates originating from different cells of the same landfill in Sweden. The objective of the study was to determine the uptake, or release, of metals and dissolved organic carbon (DOC) during a leaching test using the pine bark filter material with the five different landfill leachates. Furthermore the change of toxicity after treatment was studied using a battery of aquatic bioassays assessing luminescent bacteria (Vibrio fischeri) acute toxicity (30-min Microtox®), immobility of the crustacean Daphnia magna, growth inhibition of the algae Pseudokirchneriella subcapitata and the aquatic plant Lemna minor; and genotoxicity with the bacterial Umu-C assay. The results from the toxicity tests and the chemical analysis were analyzed in a Principal Component Analysis and the toxicity of the samples before and after treatment was evaluated in a toxicity classification. The pine bark filter material reduced the concentrations of metal contaminants from the landfill leachates in the study, with some exceptions for Cu and Cd. The Zn uptake of the filter was high for heavily contaminated leachates (≥73%), although some desorption of zinc occurred in less contaminated waters. Some of the leachates may require further treatment due to discharge into a natural recipient in order to reduce the risk of possible biological effects. The difference in pH changes between the different leachates was probably due to variations in buffering capacity, affected by physicochemical properties of the leachate. The greatest desorption of phenol during filtration occurred in leachates with high conductivity or elevated levels of metals or salts. Generally, the toxicity classification of the leachates implies that although filter treatment with pine bark removes metal contaminants from the leachates effectively, it does not alter leachate toxicity noticeably. The leachates with the highest conductivity, pH and metal concentrations are most strongly correlated with an increased toxic response in the score plots of both untreated and treated leachates. This is in line with the toxicity classification of the leachate samples. The results from this study highlight the importance of evaluating treatment efficiency from the perspective of potential recipient effects, rather than in terms of residual concentrations of individual contaminants when treating waters with a complex contamination matrix, such as landfill leachates.     

Land application of biosolids. Soil response to different stabilization degree of the treated organic matter

The effect of land application of biosolids on an agricultural soil was studied in a 2-month incubation experiment. The soil microbial biomass and the availability of heavy metals in the soil was monitored after the application of four different composting mixtures of sewage sludge and cotton waste, at different stages of composting. Land application caused an increase of both size and activity of soil microbial biomass that was related to the stabilization degree of the composting mixture. Sewage sludge stabilization through composting reduced the perturbance of the soil microbial biomass. At the end of the experiment, the size and the activity of the soil microbial biomass following the addition of untreated sewage sludge were twice those developed with mature compost. For the mature compost, the soil microbial biomass recovered its original equilibrium status (defined as the specific respiration activity, qCO2) after 18 days of incubation, whereas the soil amended with less stabilized materials did not recover equilibrium even after the two-month incubation period. The stabilization degree of the added materials did not affect the availability of Zn, Ni, Pb, Cu, Cr and Cd in the soil in the low heavy metal content of the sewage sludge studied. Stabilization of organic wastes before soil application is advisable for the lower perturbation of soil equilibria status and the more efficient C mineralization.     

Effect of sewage sludge or compost on the sorption and distribution of copper and cadmium in soil

The application of biosolids such as sewage sludge is a concern, because of the potential release of toxic metals after decomposition of the organic matter. The effect of application of sewage sludge (Sw) and compost (C) to the soil (S) on the Cu and Cd sorption, distribution and the quality of the dissolved organic matter (DOM) in the soil, was investigated under controlled conditions. Visible spectrophotometry, infrared spectroscopy, sorption isotherms (simple and competitive sorption systems), and sequential extraction methods were used. The E4/E6 (lambda at 465 and 665 nm) ratio and the infrared spectra (IR) of DOM showed an aromatic behaviour in compost-soil (C-S); in contrast sewage sludge-soil (Sw-S) showed an aliphatic behaviour. Application of either Sw or C increased the Cu sorption capacity of soil. The Cd sorption decreased only in soil with a competitive metal system. The availability of Cu was low due to its occurrence in the acid soluble fraction (F3). The Cu concentration varied in accordance with the amounts of Cu added. The highest Cd concentration was found in the exchangeable fraction (F2). The Sw and C applications did not increase the Cd availability in the soil.     

Application of sewage sludge compost on highway embankments

More and more sewage sludge is being produced in China. Safe and economical methods for sewage sludge disposal should be found considering the increase in sewage treatment. In order to verify the feasibility of sludge disposal on newly built highway embankments, five treatments (0, 15, 30, 60 and 120 tons ha⁻¹) of sewage sludge compost (SSC) were added to a silty-clay embankment soil on the Xi-Huang highway. The results showed that amendment with SSC increased soil available N, available P, organic matter, cation exchange capacity, and water content, and decreased soil bulk density. Application of SSC enhanced ryegrass growth and reduced runoff and soil erosion. Heavy metal losses from sediments in runoff remained constant or decreased relative to the control until a rate of 60 tons ha⁻¹ was exceeded, when heavy metal losses appeared to increase.     

Solid-phase fluorescence spectroscopy to characterize organic wastes

The production of solid organic waste (SOW) such as sewage sludge (SS) or municipal solid waste (MSW) has been continuously increasing in Europe since the beginning of the 1990'. Today, the European Union encourages the stabilization of these wastes using biologic processes such as anaerobic digestion and/or composting to produce bio-energy and organic fertilizers. However, the design and management of such biologic processes require knowledge about the quantity and quality of the organic matter (OM) contained in the SOW. The current methods to characterize SOW are tedious, time-consuming and often insufficiently informative. In this paper, we assess the potential of solid-phase fluorescence (SPF) spectroscopy to quickly provide a relevant characterization of SOW. First, we tested well known model compounds (tryptophan, bovine serum albumin, lignin and humic acid) and biologic matrix (Escherichia coli) in three dimensional solid-phase fluorescence (3D-SPF) spectroscopy. We recorded fluorescence spectra from proteinaceous samples but we could not record the fluorescence emitted by lignin and humic acid powders. For SOW samples, fluorescence spectra were successfully recorded for MSW and most of its sub-components (foods, cardboard) but impossible for SS, sludge compost (SC) and ligno-cellulosic wastes. Based on visual observations and additional assays, we concluded that the presence of highly light-absorptive chemical structures in such dark-colored samples was responsible for this limitation. For such samples, i.e. lignin, humic acid, SS, SC and ligno-cellulosic wastes, we show that laser induced fluorescence (LIF) spectroscopy enables the acquisition of 2D fluorescence spectra.     

Air permeability of compost as related to bulk density and volumetric air content.

Compost air permeability controls air flow through compost during composting or when using compost as biofilter material. Air permeability is therefore an important characteristic of compost. The relationships between air permeability (k(a)) in compost and compost dry bulk density (rho b), gravimetric water content (omega), and volumetric air content (epsilon) was investigated for two types of composts. The composts used were produced from a digested sewage sludge-straw mixture and from garden waste and measurements were conducted on sieved and repacked 100 cm3 compost samples. Results showed a linear relation between log(k(a)) and rho b at constant values of omega for both composts, indicating an exponential relationship between k(a) and rho b. The slopes of these relationships generally became more negative with increasing rho b. The results further showed a linear relationship between log(k(a)) and log(epsilon) for both composts as also often observed for soils. It was observed that the log(k(a)) and log(epsilon) relationships for the garden waste compost all intercepted at the same location despite having very different slopes. This means that it is possible to predict the entire k(a)-epsilon relationship using only one measurement of corresponding (k(a), epsilon) for garden waste. It was not possible to determine whether this was also the case for the sewage sludge compost due to difficulties in sample preparation at low and high water content.     

Synthesis and characterization of drinking water treatment plant sludge-incorporated Portland cement

Kinetic analysis of thermally activated phase transformations in drinking water treatment plant (DWTP) sludge suggests its applicability in the materials of construction. The suggested prediction has already been verified on the sludge-based bricks. The present study deals with incorporating the same sludge in the raw meal for the synthesis of Portland cement clinkers. For this purpose, two raw meals are prepared with varying sludge loadings. The sludge effect on reactivity of the crude mixture is evaluated on the basis of the free lime content sintered at various elevated temperatures. The results of chemical and mineralogical and scanning electron microscopic analyses reveal fine mineralogical contents of Portland clinkers calcined at 1450 and 1500 °C. Moreover, the cements prepared from these clinkers by the introduction of certain proportions of gypsum, depict significant durability. The obtained results elucidate that the studied DWTP sludge-incorporated Portland cement shows considerable potential to be commercialized.     

Mercury emission from sewage sludge incineration in Japan

Sewage sludge contains trace amounts of mercury, and sewage sludge incineration is a major source of mercury emissions. However, relatively few studies have reported on mercury emissions from sewage sludge incineration. Consequently, data on emissions from sewage sludge incinerators must be updated to estimate current emissions of mercury. In this study, we examined mercury emissions and speciation using continuous mercury analyzers in two incinerators. The mercury concentrations in stack gas from facilities A and B were 36.6 and 21.1???g/Nm³, respectively. As a result, the emission rate was calculated to be 0.282?C0.750?g/ton-dry sludge. Considering the total amount of sewage sludge incinerated in Japan, the mercury emissions from sewage sludge incinerators were estimated to be 0.49?C1.31?tons/year.     

Effects of composted sewage sludge on microbial biomass, activity and pine seedlings in nursery forest

The investigation was carried out in a 2 year experiment to evaluate the benefits and hazards of the use of composted sewage sludge as a restoration agent for the soil of the nursery forest intended for growing Pinus sylvestris seedlings. The grey forest soil (Haplic Greyzem) was amended with compost at the 25, 50, 75, 100, 150 and 175 t ha(-1) application rates on a dry matter basis. The organic matter content increased with the increase in sludge amendment as well as the metal content. However, the concentrations of individual metals were below the current limits established for Russia and European countries. Sludge amendments enhanced the germination and decreased the mortality of the seedlings. The effects were more obvious for the soil with the highest sludge treatment. The beneficial effects on the biomass of seedlings and the height of the shoots as well as on the length of the roots of the pine seedlings were greater in plots with the highest rates of composted sludge. The application of composted sludge to soil was followed by an increase in microbial biomass and to a lesser extent in basal respiration. In the absence of any detrimental effect on microorganisms, this study lends support to using composted sewage sludge as the organo-mineral fertilizer for the soil of nursery forest.