Xenobiotic organic compounds in leachates from ten Danish MSW landfills--chemical analysis and toxicity tests

A monitoring program comprising chemical analysis and biological toxicity testing of leachate samples from 10 Danish landfills (six engineered and four uncontrolled) revealed the presence of 55 different xenobiotic organic compounds (XOCs) and 10 degradation products of XOCs. The compounds belong to the following groups: BTEX, C3-benzenes, bicyclo compounds, napthalenes, chlorinated aliphatics, phenols (chloro-, methyl-, dimethyl, nonyl-), pesticides, and phthalates. Concentrations of single XOCs ranged from <0.1 to 2220 microg/L. A pesticide screening including 101 different compounds resulted in detection of 18 pesticides and three degradation products. The findings of degradation products of toluene, phenols, phthalates, pesticides, and nonylphenol ethoxylates show that degradation occurred inside the landfills. In biotests with bacteria and algae it was found that the non-volatile organic compounds were toxic as the samples only needed to be pre-concentrated from 1.3 to 9.4 times to give 50% inhibition of the test organisms. One of the ten samples proved to be genotoxic in the umuC test after 141 times pre-concentration. A major part of the organic chemicals causing toxicity remains unknown and it is recommended to combine chemical analyses and biotests in future monitoring programs.     

Assessment of toxicity reduction after metal removal in bioleached sewage sludge

Sewage sludge can be applied to land to supply and recycle organic matter and nutrients. Trace elements in sludge, however, may accumulate in the soil with repeated sludge applications. Reducing metal content may therefore reduce the adverse effects of sludge application. The objective of this study was to evaluate the efficiency of bioleaching technology in reducing metal content and toxicity as measured by a battery of terrestrial and liquid-phase bioassays. Sludge-soil mixtures simulating the application of sludge to land were tested by means of terrestrial bioassays, barley (Hordeum vulgare L.) seed germination (5 d) and sprout growth (14 d), lettuce (Lactuca sativa) seed germination (5 d), and worm (Eisenia andrei) mortality (14 d). Liquid-phase bioassays, Microtox (Vibrio fischeri, 15 min), lettuce root elongation (L. sativa, 5 d), cladoceran mortality (Daphnia magna, 48 h), and SOS Chromotest (Escherichia coli) were used after elutriation of the sludge. Comparison of the bioassay results (except for D. magna) before and after treatment demonstrated that this bioleaching process reduced both sludge toxicity and metal content. In addition, lower Cu and Zn concentrations found in barley sprouts following treatment supported the assumption that the bioleaching process, by decreasing metal content and bioavailability, reduced sewage sludge toxicity. This study also emphasized the interest of using ecotoxicological bioassays for testing biosolids. In particular, the terrestrial bioassays after simulation of land application and the Microtox test after sludge elutriation proved to be the most appropriate procedures.     

Fluorescence of leachates from three contrasting landfills

Landfill leachates are composed of a complex mixture of degradation products including dissolved organic matter, which includes a wide range of potentially fluorescent organic molecules and compounds. Here we investigate the excitation-emission matrix fluorescence of landfill leachates from three contrasting landfill sites. Landfill fluorescence properties are all characterized by intense fluorescence at lambda(ex) =220-230nm, and lambda(em) =340-370nm which we suggest derives from fluorescent components of the Xenobiotic Organic Matter fraction such as naphthalene, as well as at lambda(ex) =320-360nm, and lambda(em) =400-470nm from a higher molecular weight fulvic-like fraction. Landfill leachates are characterized by intense fluorescence, with approximately 10(2) intensity units of fluorescence at lambda(ex)=220-230nm, and lambda(em)=340-370nmmg(-1) of total organic carbon, demonstrating leachate detection limits of <0.1mgl(-1) total organic carbon. We demonstrate that for all landfill sites, leachate fluorescence intensity has a strong correlation with ground water quality determinants ammonia, total organic carbon and biochemical oxygen demand. We investigate both within-site and between-site leachate fluorescence properties, and demonstrate that although there is significant within-site variability, leachates from all 3 sites can be statistically discriminated using just fluorescence properties (65% success rate) or with a combination of fluorescence and basic geochemical parameters (85%). Our findings suggest that fluorescence can be used as a rapid and sensitive tracer of leachate contamination of ground water, as well as help discriminate, together with geochemical determinants, leachates from different landfill sources.     

Partial ammonium oxidation to nitrite of high ammonium content urban landfill leachates

In an effort to treat N-rich streams in a more sustainable way, recent years have seen the development of new technologies, most of which are based on autotrophic denitrification via nitrite (anammox). In order to attain a suitable influent for that process, the wastewater must be treated by partially oxidising the ammonium to nitrite. In that aspect, this article presents the start-up and operation of a Partial Nitritation Sequencing Batch Reactor (PN-SBR) treating urban landfill leachates. Stable partial nitritation has been reached treating high ammonium loads (1-1.5 kg Nm(-3)d(-1)), demonstrating the feasibility of this technology as a previous step of anammox process. This study has also given away the importance of pH influence over ammonium oxidising bacteria (AOB) activity, thus it has been possible to determine the values of the half inhibition constants for free ammonia (k(I,FA)=605.48+/-87.18 mg N-NH L(-1)) and free nitrous acid (k(I,FNA)=0.49+/-0.09 mg N-HNO2 L(-1)), as well as the half-saturation constant for bicarbonate (k(HCO3-) = 0.01 +/- 0.16 mg CL(-1)).     

Assessment of the formation of inorganic oxidation by-products during the electrocatalytic treatment of ammonium from landfill leachates

This work investigates the formation of oxidation by-products during the electrochemical removal of ammonium using BDD electrodes from wastewaters containing chlorides. The influence of the initial chloride concentration has been experimentally analyzed first, working with model solutions with variable ammonium concentration and second, with municipal landfill leachates. Two different levels of chloride concentration were studied, i) low chloride concentrations ranging between 0 and 2000 mg/L and, ii) high chloride concentrations ranging between 5000 and 20,000 mg/L. Ammonium removal took place mainly via indirect oxidation leading to the formation of nitrogen gas and nitrate as the main oxidation products; at high chloride concentration the formation of nitrogen gas and the rate of ammonium removal were both favored. However, chloride was also oxidized during the electrochemical treatment leading to the formation of free chlorine responsible of the ammonium oxidation, together with undesirable products such as chloramines, chlorate and perchlorate. Chloramines appeared during the treatment but they reached a maximum and then started decreasing, being totally removed when high chloride concentrations were used. With regard to the formation of chlorate and perchlorate once again the concentration of chloride exerted a strong influence on the formation kinetics of the oxidation by-products and whereas at low chloride concentrations, chlorate appeared like an intermediate compound leading to the formation of perchlorate, at high chloride concentrations chlorate formation was delayed significantly and perchlorate was not detected during the experimental time. Thus this work contributes first to the knowledge of the potential hazards of applying the electro-oxidation technology as an environmental technology to deal with ammonium oxidation under the presence of chloride and second it reports efficient conditions that minimize or even avoid the formation of undesirable by-products.     

Removal of organics from leachates by anaerobic filter

A laboratory-scale study was conducted on two anaerobic filters at several loading rates and four hydraulic detention times. Feed substrates were landfill leachates taken from a recently opened landfill (Keele Valley) and from an older site (Brock North) which had been closed for about 8 years. The strong raw leachate from the new landfill had a COD of 14,000 mg l⁻¹, a BOD/COD ratio of 0.7 and a COD/P value of 17,900. The partially stabilized leachate from the older landfill had a COD of only 3750 mg l⁻¹, a BOD/COD ratio of 0.3 and a COD/P value of 30,640.Results from the treatment of the two leachates were compared with those from a previous study of a “mature” landfill (Beare Road). It was demonstrated that the anaerobic filter could reduce the COD of leachate from landfills of different ages by 90%, at loading rates of 1.26–1.45 kg COD m⁻³ d⁻¹. Total biogas production ranged between 400 and 500 l gas kg⁻¹ COD destroyed and methane content between 75 and 85%. No phosphorus addition was required over the loading range studied.     

Mono- and diesters from o-phthalic acid in leachates from different European landfills

Leachates from 17 different landfills in Europe were analysed with respect to phthalates, i.e. phthalic acid diesters (PAEs) and their degradation products phthalic acid monoesters (PMEs) and ortho-phthalic acid (PA). Diesters are ubiquitous and the human possible exposure and potential to human health and environment has put them in focus. The aim of this study was to elucidate whether monoesters and phthalic acid could be traced in landfill leachates and in what concentrations they may be found. The results showed that phthalates were present in the majority of the leachates investigated. The monoesters appeared from 1 to 20 microg/L and phthalic acid 2-880 microg/L (one divergent value of 19 mg phthalic acid/L). Their parental diesters were observed from 1 to 460 microg/L. These observed occurrences of degradation products, of all diesters studied, support that they are degraded under the landfill conditions covered by this study. Thus, we have presented strong evidences to conclude that microorganisms in landfills degrade diesters released from formulations in a variety of products, including polyvinyl chloride (PVC) species.     

Removal of non-biodegradable organic matter from landfill leachates by adsorption

Leachates produced at the La Zoreda landfill in Asturias, Spain, were recirculated through a simulated landfill pilot plant. Prior to recirculation, three loads of different amounts of Municipal Solid Waste (MSW) were added to the plant, forming in this way consecutive layers. When anaerobic digestion was almost completed, the leachates from the landfill were recirculated. After recirculation, a new load of MSW was added and two new recirculations were carried out. The organic load of the three landfill leachates recirculated through the anaerobic pilot plant decreased from initial values of 5108, 3782 and 2560 mg/l to values of between 1500 and 1600 mg/l. Despite achieving reductions in the organic load of the leachate, a residual organic load still remained that was composed of non-biodegradable organic constituents such as humic substances. Similar values of the chemical oxygen demand (COD) were obtained when the landfill leachate was treated by a pressurised anoxic-aerobic process followed by ultrafiltration. After recirculation through the pilot plant, physico-chemical treatment was carried out to reduce the COD of the leachate. The pH of the leachate was decreased to a value of 1.5 to precipitate the humic fraction, obtaining a reduction in COD of about 13.5%. The supernatant liquid was treated with activated carbon and different resins, XAD-8, XAD-4 and IR-120. Activated carbon presented the highest adsorption capacities, obtaining COD values for the treated leachate in the order of 200mg/l. Similar results were obtained when treating with activated carbon, the leachate from the biological treatment plant at the La Zoreda landfill; in this case without decreasing the pH.     

Occurrence and distribution of organotin compounds in leachates and biogases from municipal landfills

The occurrence and distribution of organotin compounds (OTC) in effluents from two different landfills were investigated through the combination of three different analytical methodologies. In this way, the determination of the volatile OTC in biogases, the dissolved volatile and dissolved ionic organotin species in leachates was carried out using these complementary approaches. In leachates, up to nine OTC (i.e. methyltin, ethyltin, butyltin and mixed methyl-ethyltins) were detected at concentrations ranging from 0.01 to 6.5 microg (Sn)L(-1), which represents 1-38% of the total tin concentration. In biogases, five volatile tin species (i.e. methyltin, mixed methyl-ethyltin and ethyltin) were determined at significant concentrations reaching up to 25 microg (Sn)m(-3). The occurrence of the overall identified species is explained by both organotin-containing waste and endogenous alkylation pathways. Two parameters seem to significantly influence the effluent OTC composition: first, wet depositions both induce leachate dilution and alter methylation/ethylation mechanisms; second, evolution of the waste degradation stage yields different volatilisation mechanisms (i.e. permethylation or perethylation). The results obtained in this work outline the diversity and variability of the organotin contamination routes provided by multiple pathways. These phenomena can lead to the release of biologically harmful species in the environment if no efficient effluent treatment is applied.     

Characterization of sanitary landfill leachates

Composition of leachates from some sanitary landfills in Norway and in the U.S.A. is described. The wide range of compositions found was mainly attributed to the efficiencies of preventing water to enter the fills.

Organic acids were found to contribute almost 90% of the total organics in the high strength leachates. The ratio of carbonaceous BOD to COD increased significantly with the concentrations of organics. Thus a better biological treatability is expected for the high strength leachates. High concentrations of nitrogen mainly as ammonia prevailed in all the samples while the concentrations of phosphorus were low. Of the heavy metals, iron were high in all the leachates, zinc was found to be the next highest. The concentrations of chromium, nickel, copper, cadmium and lead were low.     

Assessment of metal mobility in dredged harbour sediments from Barcelona, Spain

In order to assess heavy metal mobility in dredged harbour sediments, six superficial sediment samples covering a range of pollution levels and environments were collected in Barcelona Harbour. Samples were characterised in terms of major compounds (Al, Ca, Fe, Mn, Si, Ti, Mg, K and Na); total C, N and S contents; organic matter; and water content. Pseudo-total trace metal contents were assessed after aqua regia digestion (ISO 11466:1995). The modified BCR three-step sequential extraction procedure (BCR-SEP) was applied, and both major compounds (Al, Ca, Fe and Mn) and trace metals (Cd, Cr, Cu, Ni, Pb and Zn) were determined in the different extracts. Both the pseudo-total digestion method and the BCR-SEP were validated using two sediment certified materials from lakes (BCR CRM 701 and BCR CRM 601). The highest metal concentrations were observed in one of the sampling points which receives an urban discharge. The observed mobility order (percentage of metal extracted in the first step) of the six trace metals studied was Cd>Zn>Pb>Cu>Ni>Cr. The good agreement observed with the results obtained as the sum of the four steps (extractable+residue) and the pseudo-total content shows that laboratory working conditions were under control.     

Complexation and toxicity of copper and the free metal bioassay technique

The concentrations of free and total copper toxic to Daphnia and guppies were determined in inorganic media with and without addition of various concentrations of β-alanine, glycine, glutamic acid or Tris. Free copper concentrations were determined using a cupric ion electrode. Stability constants calculated for each of the detected complexes compared favourably with previously published values, with the possible exception of the Cu(OH)₂ complex. Free copper concentrations in solutions equally toxic to Daphnia were observed to vary greatly, primarily because of the toxicity of copper amino acid complexes to this organism. The copper/amino acid complexes were, nevertheless, less toxic than the free copper ions. The copper/β-alanine complex was observed to be less toxic to guppies than to Daphnia, indicating a difference in sensitivity to different copper complexes in different organisms. Copper/Tris complexes were found to be only slightly toxic to both Daphnia and guppies. A bioassay technique for determining free copper concentrations by comparing copper toxicity before and after addition of Tris was tested and verified. Although free metal concentrations can be determined from properly conducted bioassays, the variation in free metal concentration in equally toxic solutions demonstrates that free metal concentrations cannot be calculated by simply comparing metal toxicity in a test solution with toxicity of the same metal in a standard solution with known free metal concentration, unless it is known that no complexes are present in the test solution which can form toxic complexes with the metal.     

Dynamics of metal availability and toxicity in historically polluted floodplain sediments

Many floodplains contain high concentrations of sediment associated contaminants that might be subjected to large changes in terms of mobility, transformation and bioavailability. Therefore, this study describes 1) changes in the redox conditions and the mobility of metals in artificially uncovered polluted floodplain sediments, 2) metal uptake by organisms and 3) colonization, succession and functioning of benthic algae on these sediments. Flooding caused long term changes in redox potential (Eh) profiles. In top layers strong gradients in redox potential established quickly, while in deeper layers changes occurred more gradually. The availability of copper as measured by Diffusive Gradients in Thinfilms (DGT) showed a consistent relationship with fluctuations in Eh. However, this relationship was restricted to deeper layers in the sediment. Within 1 week high amounts of total copper were immobilized. Differences in total copper concentrations between polluted and clean sediments became only partially apparent when comparing the available copper fraction (DGT-Cu). Introduced Tubifex shows only marginal differences in levels of accumulated Cu. Colonization, growth and succession of algal communities on polluted sediments was not impaired, most likely due to low bioavailability. It is concluded that changing environmental conditions, such as flooding, can result in stable chemical conditions with low a availability of metals and hence in a diminution of actual ecological risks.     

Complexation characteristics of sanitary landfill leachates

The complexation of cadmium by organic components of sanitary landfill leachates was investigated using ion-exchange and specific ion electrode methods. Four Southern Ontario leachates were all found to be capable of complexing cadmium, to varying degrees. The complexing ability associated with certain molecular weight fractions was studied. In one leachate, complexation was mainly attributed to low (<500) molecular weight compounds. Their behaviour was consistent with that of simple carboxylic acids. In another leachate, high (> 10,000) molecular weight compounds contributed significantly to complexation. Their behaviour suggested that they might contain phenolic hydroxyl groups having a stability constant towards cadmium of the order of 10⁵. It was concluded that the role of complexation in determining the fate of metals in sanitary landfill leachates depended upon several factors whose importance had not yet been adequately investigated or reported in the literature.     

Heavy metal content of oysters from the Lynher Estuary,U.K.

The concentrations of As, Cd, Cu, Hg, Pb and Zn have been determined in oysters and sediments from the Lynher Estuary, U.K. The sediments contained high levels of Cu, Fe, Pb and Zn probably associated with run off from a metalliferous catchment area and high Hg associated with a local sewage input. In contrast, the analyses of the oyster tissue showed that only Cu and Zn were concentrated in the flesh. The majority of samples contained coliform bacteria in excess of 1000 organisms per ml of tissue. It is concluded that the quality of the oysters from this fishery was limited by the bacteriological cleanliness rather than toxic metal content.     

Assessment of the fire toxicity of building insulation materials

A significant element in the cost of a new building is devoted to fire safety. Energy efficiency drives the replacement of traditional building materials with lightweight insulation materials, which, if flammable can contribute to the fire load. Most fire deaths arise from inhalation of toxic gases. The fire toxicity of six insulation materials (glass wool, stone wool, expanded polystyrene foam, phenolic foam, polyurethane foam and polyisocyanurate foam) was investigated under a range of fire conditions. Two of the materials, stone wool and glass wool failed to ignite and gave consistently low yields of all of the toxic products. The toxicities of the effluents, showing the contribution of individual toxic components, are compared using the fractional effective dose (FED) model and LC₅₀ (the mass required per unit volume to generate a lethal atmosphere under specified conditions). For polyisocyanurate and polyurethane foam this shows a significant contribution from hydrogen cyanide resulting in doubling of the overall toxicity, as the fire condition changes from well-ventilated to under-ventilated. These materials showed an order of increasing fire toxicity, from stone wool (least toxic), glass wool, polystyrene, phenolic, polyurethane to polyisocyanurate foam (most toxic).     

Effects of carbon dioxide deficiency and metal toxicity on biological oxygen demand

In this study, the effects of carbon dioxide (CO₂) deficiency on the biological growth under respirometric conditions, first‐ and second‐order biological oxygen demand (BOD) progressions using two different BOD measurement techniques and metal toxicity effects on the respirometric BOD are investigated. The effects of CO₂ deficiency in the growth of bacteria and related effects on the first‐ and second‐stage BOD progressions are investigated using various media with respirometers in comparison with the BOD dilution method. CO₂ deficiency causes significant retardations on the growth of bacteria and the second‐stage respirometric BOD values are suppressed. CO₂ seems to be an essential nutrient for the growth of microorganisms and for the oxygen uptake progressing rates. HgCl₂, HgSO₄, CuSO₄, K₂Cr₂O₇, ZnSO4 and Al₂(SO₄)₃ inorganic metal compounds cause significant retardations in the respirometric BOD values obtained from a synthetic autotrophic medium. Effects are found to be dependent on the applied concentrations of these chemicals in the medium.     

Stabilized leachates: ozone-activated carbon treatment and kinetics

Ozone has been used as a pre-oxidation step for the treatment of stabilized leachates. Given the refractory nature of this type of effluents, the conversion of some wastewater quality parameters has been moderate after 1 h of ozonation (i.e. 30% chemical oxygen demand (COD) depletion). Ozone uptake was calculated in the interval 1.3–1.5 g of ozone per gram of COD degraded. An optimum dose of ozone has been experienced in terms of biodegradability of the processed effluent (60 min of treatment, 1×10⁻³ molL⁻¹ ozone inlet feeding concentration and 50 Lh⁻¹ gas flow-rate). pH and other typical hydroxyl radical generator systems exerted no influence on the efficiency of the process, suggesting the negligible role played by the indirect route of oxidation (generation of hydroxyl radicals). The ozonated effluent was thereafter treated in a second adsorption stage by using a commercial activated carbon. Removal levels up to 90% of COD in approximately 120 h were experienced for adsorbent dosages of 30 gL⁻¹. Both steps, the single ozonation and the adsorption stage have been modelled by using different pseudoempirical models.     

Photodegradation of roxarsone in poultry litter leachates

Arsenic compounds have been used extensively in agriculture in the US for applications ranging from cotton herbicides to animal feed supplements. Roxarsone (3-nitro-4-hydroxyphenylarsonic acid), in particular, is used widely in poultry production to control coccidial intestinal parasites. It is excreted unchanged in the manure and introduced into the environment when litter is applied to farmland as fertilizer. Although the toxicity of roxarsone is less than that of inorganic arsenic, roxarsone can degrade, biotically and abiotically, to produce more toxic inorganic forms of arsenic, such as arsenite and arsenate. Experiments were conducted on aqueous litter leachates to test the stability of roxarsone under different conditions. Laboratory experiments have shown that arsenite can be cleaved photolytically from the roxarsone moiety at pH 4-8 and that the degradation rate increases with increasing pH. Furthermore, the rate of photodegradation increases with nitrate and natural organic matter concentration, reactants that are commonly found in poultry-litter-water leachates. Additional photochemical reactions rapidly oxidize the cleaved arsenite to arsenate. The formation of arsenate is not entirely undesirable, because it is less mobile in soil systems and less toxic than arsenite. A possible mechanism for the degradation of roxarsone in poultry litter leachates is proposed. The results suggest that poultry litter storage and field application practices could affect the degradation of roxarsone and subsequent mobilization of inorganic arsenic species.