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.     

Dissolved organic matter in leachate from different treatment processes

The main objectives of this study were to investigate the characteristics of dissolved organic matter (DOM) extracted from the leachate of different treatment process using the chemical and spectroscopic analysing methods. The humic acid (HA), fulvic acid (FA) and hydrophilic (HyI) were isolated and purified by the XAD-8 resin combined with the cation exchange resin method. The analytical results of fluorescence excitation-emission matrix spectroscopy (EEMs) revealed that the fluorescence peaks were protein-like fluorescence for equalization basin and discharge of reverse osmosis (RO), while the fluorescence peaks for second sedimentation tank were humic-like and fulvic-like fluorescence. Moreover, the results also showed that protein-like organic matter are readily removed by biological process and HA and FA can be removed by RO process. Elemental analysis indicated that the nitrogen content in these isolated fractions followed: HA>HyI>FA. The information on the characteristics of DOM indicated important role in optimization of leachate treatment processes.     

Removal and transformation of recalcitrant organic matter from stabilized saline landfill leachates by coagulation-ozonation coupling processes

The Bordo Poniente sanitary landfill in Mexico City currently receives 11,500 ton/day of solid wastes. The landfill has been in operation since 1985, in what was formerly Texcoco Lake, now a dried-up lakebed. The physico-chemical characteristics of the leachate generated by this particular landfill are altered by the incorporation of freatic saline water present in the area. This paper reports the results from a study evaluating coagulation and ozonation as alternative processes for removing and transforming recalcitrant organic matter from stabilized saline landfill leachate. Coagulation with ferric sulfate was found to remove up to 67% of COD and 96% of leachate color. The remaining 33% COD was removed with ozone. Recalcitrant organic matter removal by ozonation is limited by the reaction kinetic due mainly to ozone's low reactivity with the organic compounds present in the leachates (amines, amides, alcohols, aliphatic compounds, and carboxylic acids). However, ozone contributes greatly to changing the recalcitrant characteristics of organic matter. Leachate biodegradability was found to be significantly enhanced through ozonation: BOD(5) values reach 265%, and the BOD(5)/COD ratio increases from 0.003 to 0.015. Infrared analysis of ozonated leachates shows that the main by-products of recalcitrant organic matter ozonation are an increase in the hydroxyl and carboxylic groups, and the presence of aldehydes groups.     

Molecular characterization of effluent organic matter identified by ultrahigh resolution mass spectrometry

Effluent dissolved organic matter (EfOM) collected from the secondary-treated wastewater of the Orange County Sanitation District (OCSD) located in Fountain Valley, California, USA was compared to natural organic matter collected from the Suwannee River (SRNOM), Florida using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Furthermore, the two different treatment processes at OCSD, activated sludge and trickling filter, were separately investigated. The blend of these two effluents was further evaluated after it had passed through the microfiltration process of the Advanced Water Purification Facility (AWPF) at Orange County Water District (OCWD). EfOM contained 872 different m/z peaks that were unambiguously assigned to exact molecular formulae containing a single sulfur atom and carbon, hydrogen and oxygen atoms (CHOS formulae). In contrast, the SRNOM sample only contained 152 CHOS formulae. The trend in CHO molecular compositions was opposite with 2500 CHO formulae assigned for SRNOM but only about 1000 for EfOM. The CHOS-derived mass peaks with highest abundances in EfOM could be attributed to surfactants such as linear alkyl benzene sulfonates (LAS), their co-products dialkyl tetralin sulfonates (DATS) and their biodegraded metabolites such as sulfophenyl carboxylic acids (SPC). The differences between the treatments were found minor with greater differences between sampling dates than treatment methods used.     

Structural investigations of aquatic humic substances by pyrolysis-field ionization mass spectrometry and pyrolysis-gas chromatography/mass spectrometry

The present state-of-the-art in structural investigations of aquatic humic substances and their fractions such as fulvic and humic acids by pyrolysis-field ionization mass spectrometry is outlined. An integrated approach to interpretation uses complementary data of elemental analysis, functional group determinations, Cu²⁺-complexation, H⁺-capacity and results from u.v.-vis- and FT-i.r.-spectroscopy. Proposed building blocks of the molecular structure are supported by chromatographic investigations using Curie-point Py-GC/MS and the available literature reports. The potential and limitation of the applied methodology are discussed.     

New standards for the determination of geosmin and methylisoborneol in water by gas chromatography/mass spectrometry

Deuterium labelled geosmin and methylisoborneol (MIB) have been synthesized and evaluated as internal standards in the determination of geosmin and MIB in water by closed loop stripping followed by gas chromatography/mass spectrometry (GC/MS). The labelled standards were compared with chloroalkanes added as internal standards either at the time of sampling or immediately before closed loop stripping. When added at sampling time, the new standards enabled accurate determination of the geosmin and MIB present initially, even when the samples were analysed as much as 3 weeks later. The new standards gave better precision and accuracy than the chloroalkanes and overcame the underestimation of initial analyte concentration which usually results from losses of analyte through adsorption, volatilisation, biodegradation etc. during sample storage. Geosmin had a limit of detection of<0.1ng/l and 1 ng/lwas determined with a coefficient of variation (CV) of 1.2% (n = 5). MIB was determined at 1 ng/l with a CV of 3.5% (n = 5).     

Interactions of diuron with dissolved organic matter from organic amendments

Diuron is frequently detected in some drinking water reservoirs under the Burgundy vineyards, where organic amendments are applied. The environmental effect of these amendments on pesticide transport is ambiguous: on the one hand it could enhance their retention by increasing soil organic carbon content; on the other hand, dissolved organic matter (DOM) could facilitate their transport. Elutions were performed using columns packed with glass beads in order to investigate DOM-diuron interactions, and the possible co-transport of diuron and DOM. Four organic amendments (A, B, C and D) were tested; C and D were sampled at fresh (F) and mature (M) stages. An increase in diuron leaching was observed only for A and D_F amendments (up to 16% compared to the DOM-free blank samples), suggesting a DOM effect on diuron transport. These results could be explained by the higher DOM leaching for A and D_F compared to B, C_F, C_M and D_M increasing diuron-DOM interactions. These interactions seem to be related to the aromatic and aliphatic content of the DOM, determining formation of hydrogen and non-covalent bonds. The degree of organic matter maturity does not seem to have any effect with amendment C, while a reduction in diuron leaching is observed between D_F and D_M. After equilibrium dialysis measurement of diuron-DOM complexes, it appeared that less than 3% of the diuron applied corresponded to complexes with a molecular weight > 1000 Da. Complexes < 1000 Da could also take part in this facilitated transport.     

Organic sulfur compounds and polycyclic hydrocarbons transferred to oyster and mussel from petroleum suspension: Identification by gas chromatography and capillary mass chromatography

An attempt was made to determine the organic sulfur compounds usually contained in crude oil as markers of oil pollution in shellfish. The oyster (Crassostrea gigas) and mussel (Mytilus edulis) were maintained in a controlled laboratory environment and in water with a suspension of crude oil. Capillary column gas chromatography-mass chromatography of extracts showed the presence of organic sulfur compounds of alkyl benzothiophene (C₂C₄), dibenzothiophene and alkyl dibenzothiophene (C₁C₄). Coexistence of polycyclic aromatic hydrocarbons with organic sulfur compounds was found in oyster and mussel. The time courses of concentration ratios of organic sulfur compounds in the oyster and the mussel were determined by gas chromatography connected with flame photometric detector.     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Isolation of dissolved organic matter from the suwannee river using reverse osmosis

A portable reverse osmosis (RO) system was constructed and used to concentrate dissolved organic matter (DOM) from the Suwannee River in southeastern Georgia. Using this RO system, 150–180 1/h of river water could be processed with 90% recovery of DOM. After further cation exchange and lyophilization of the concentrated river water samples, large quantities of low-ash freeze-dried products were isolated. We highly recommend this RO method for concentration of DOM in fresh waters because (1) a very high percentage of DOM is recovered, which indicates minimal fractionation of the original sample; and (2) the process is quite rapid, which permits large quantities of DOM to be concentrated in a reasonable length of time.     

Insight into the heavy metal binding potential of dissolved organic matter in MSW leachate using EEM quenching combined with PARAFAC analysis

Dissolved organic matter (DOM) plays an important role in heavy metal migration from municipal solid waste (MSW) to aquatic environments via the leachate pathway. In this study, fluorescence excitation-emission matrix (EEM) quenching combined with parallel factor (PARAFAC) analysis was adopted to characterize the binding properties of four heavy metals (Cu, Pb, Zn and Cd) and DOM in MSW leachate. Nine leachate samples were collected from various stages of MSW management, including collection, transportation, incineration, landfill and subsequent leachate treatment. Three humic-like components and one protein-like component were identified in the MSW-derived DOM by PARAFAC. Significant differences in quenching effects were observed between components and metal ions, and a relatively consistent trend in metal quenching curves was observed among various leachate samples. Among the four heavy metals, Cu(II) titration led to fluorescence quenching of all four PARAFAC-derived components. Additionally, strong quenching effects were only observed in protein-like and fulvic acid (FA)-like components with the addition of Pb(II), which suggested that these fractions are mainly responsible for Pb(II) binding in MSW-derived DOM. Moreover, the significant quenching effects of the FA-like component by the four heavy metals revealed that the FA-like fraction in MSW-derived DOM plays an important role in heavy metal speciation; therefore, it may be useful as an indicator to assess the potential ability of heavy metal binding and migration.     

Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC

Natural organic matter (NOM) in water samples from a drinking water treatment train was characterized using fluorescence excitation emission matrices (F-EEMs) and parallel factor analysis (PARAFAC). A seven component PARAFAC model was developed and validated using 147 F-EEMs of water samples from two full-scale water treatment plants. It was found that the fluorescent components have spectral features similar to those previously extracted from F-EEMs of dissolved organic matter (DOM) from diverse aquatic environments. Five of these components are humic-like with a terrestrial, anthropogenic or marine origin, while two are protein-like with fluorescence spectra similar to those of tryptophan-like and tyrosine-like fluorophores. A correlation analysis was carried out for samples of one treatment plant between the maximum fluorescence intensities (F_max) of the seven PARAFAC components and NOM fractions (humics, building blocks, neutrals, biopolymers and low molecular weight acids) of the same sample obtained using liquid chromatography with organic carbon detection (LC-OCD). There were significant correlations (p < 0.01) between sample DOC concentration, UVA₂₅₄, and F_max for the seven PARAFAC components and DOC concentrations of the LC-OCD fractions. Three of the humic-like components showed slightly better predictions of DOC and humic fraction concentrations than UVA_254. Tryptophan-like and tyrosine-like components correlated positively with the biopolymer fraction. These results demonstrate that fluorescent components extracted from F-EEMs using PARAFAC could be related to previously defined NOM fractions and that they could provide an alternative tool for evaluating the removal of NOM fractions of interest during water treatment.     

汽油燃烧烟气的热解吸/气相色谱/质谱分析

采用热解吸进样和气相色谱/质谱联用技术(GC/MS),研究汽油燃烧产生烟气的特征组分以及不同种类载体对汽油燃烧产生的烟气特征组分的影响。实验选择93#汽油原样及其在两种典型常见载体上燃烧产生的烟气作为研究对象,在获得各样品的总离子流色谱图后,利用标准质谱库进行检索确定汽油燃烧烟气的特征组分。结果表明,汽油燃烧烟气中的最常见组分是苯、3-辛稀、邻苯二甲酸-2-甲基-庚酯、己二酸庚酯、邻苯二甲酸丁酯,其中苯和3-辛烯是汽油燃烧烟气的特征组分。热解吸进样和气相色谱/质谱联用技术对火灾现场烟气可以有效地进行鉴定,同时这种方法因为省去了萃取等实验环节而变得更简单。     

Study of pH effects on the evolution of properties of brown-water natural organic matter as revealed by size-exclusion chromatography during photocatalytic degradation

This study shows the effect of pH on the photocatalytic degradation of natural organic matter (NOM). The experiments were carried out in batch reactor (a solar UV-light simulator) with Degussa P-25 titanium dioxide (TiO₂). The NOM degradation was followed by size-exclusion chromatography for dissolved organic carbon (DOC), ultraviolet absorption and fluorescence-detection (SEC-DOC, SEC-UV₂₅₄ and SEC-Fl_254/450). Changes in pH values affected the adsorption of NOM onto TiO₂, but did not affect the photodegradation sequence of NOM. For high or low pH values, the degradation of the NOM preferentially removed the larger molecular size fraction in comparison to the middle and small molecular size fractions, resulting in the relative increase of these smaller fractions. This sequence of NOM degradation leads to the evolution of the formation potential for disinfection by-products (DBPs). Specifically, the trihalomethanes and halogenated organic compounds formation potential (THMF and AOXFP) decreased steadily.     

Analysis of triclosan and 4n‐nonylphenol in Colombian reservoir water by gas chromatography‐mass spectrometry

In this work were determined triclosan and 4n‐nonylphenol in water from a reservoir that is used to provide water to a purification plant in an important city in Colombia. The analytical methodology was validated using solid‐phase extraction and analysis by gas chromatography‐mass spectrometry (GC‐MS). The analysis by GC‐MS showed good linearity in the range of 0.05–5 μg/L for both compounds. Recoveries from 79 to 109% and standard deviations of 2.5–7.7 for low concentrations and from 3.8 to 9.6 (n = 5) for high concentrations were obtained for both compounds. In Colombia, this is the first time that these compounds have been analysed in water supplying of a drinking water treatment plant. The validated method was applied to the analysis of 27 samples collected in August 2010 in 11 locations from the reservoir and in the influent and effluent of the drinking water treatment plant. In total, seven samples were found to contain triclosan.     

Reconsidering the quantitative analysis of organic carbon concentrations in size exclusion chromatography

The evaluation of the molecular size distribution of natural organic matter (NOM) in aquatic environments via size exclusion chromatography (SEC) is important for the understanding of environmental processes such as nutrient cycling and pollutant transport as well as of technical water treatment processes. The use of organic carbon (OC) detectors has become popular in recent studies due to improved availability and quantification possibilities, which supposedly are superior to those of ultraviolet (UV) detectors. A set of 12 NOM samples was used to demonstrate the limitations of online OC detection (OCD) when analyzing complex aquatic organic matter. A novel evaluation approach for SEC data is introduced by combining the information from UV absorbance (UVA) and OCD chromatograms as well as offline total OC (t-OC) and dissolved OC-specific UVA (SUVA) measurements. It could be shown that about 70% of certain OC components were not detected with the OCD system used in this study. For the investigated samples, these types of carbon accounted for up to 72% of the t-OC, i.e. for such NOM samples quantification by OCD is not possible or at least highly questionable. The addition of an oxidant improved the overall oxidation efficiency only slightly. Most likely NOM that predominantly consists of polysaccharides and features a nominal molecular weight of 150 kg/mol or more was responsible for low OCD yields. For future applications, a further improvement of the OCD system would be worthwhile so that quantitative analytical data on the molecular size distribution of NOM and its structural characteristics such as the SUVA distribution can be obtained.     

Prediction of sand mass and organic matter distribution via in situ measured wet sediment bulk density profile

The objective of the study is to develop a spatial prediction model of sand mass and organic matter distribution in an urban stormwater holding pond using in situ measured wet sediment bulk density profile data to spatially distinguish the most likely contaminated sediment deposit areas. The wet bulk density profiles of deposited sediment at 25 locations in the Berembang (Malaysia) stormwater holding pond were measured using a single-probe nuclear density gauge. The sand and organic matter compositions of the surface sediment sample, 5 cm thickness from the bed surface, were determined. Discriminant analysis (DA) was conducted to generate two Fisher’s linear discriminant functions for the prediction of sand mass and organic matter composition areas, respectively. The linear discriminant functions generated better area classifications of surface organic matter composition compared to the sand mass distribution using wet sediment bulk density data measured at more than 15 cm depth levels.     

Characterization of natural organic matter adsorption in granular activated carbon adsorbers

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.     

有机质对土壤吸附性能的影响研究

采用了砂土与有机肥按不同比例配制有机质含量不同的4种土样为吸附剂,研究土壤对亚甲基蓝溶液的吸附性能.实验结果表明,4种土样对亚甲基蓝均有较好的吸附性能.20℃时,吸附规律较好的符合langmuir吸附等温式;pH对吸附性能有较大影响,且随有机质含量的增加,影响加强;有机质的存在可提高土壤对亚甲基蓝的吸附能力;土壤对亚甲基蓝的解析量基本随吸附量的增加而增加,但是增加的幅度非常小.     

Evaluations of the TiO2/simulated solar UV degradations of XAD fractions of natural organic matter from a bog lake using size-exclusion chromatography

This work reports on the changes in compositions of humic acids (HAs) and fulvic acids (FAs) during photocatalytic degradation. The HAs and FAs were obtained from the XAD-resin fractionation of natural-organic matter (NOM) from a bog lake (Lake Hohloh, Black Forest, Germany). Degussa P-25 titanium dioxide (TiO₂) in a suspension and a solar UV simulator (batch reactor) were used in the experiments. The photocatalytic degradation of the HAs and FAs were monitored using size-exclusion chromatography (SEC) equipped with dissolved organic carbon (DOC) and ultraviolet (UV₂₅₄) detection (SEC-DOC and SEC-UV₂₅₄) and UV–Vis spectrophotometry. The evolutions of the photocatalytic degradations of the HA and FA fractions were selective. The photocatalytic degradation started with the degradations of high molecular weight compounds with relatively high UV₂₅₄ absorbances in the HA and FA fractions to yield low molecular weight compounds showing less specific UV₂₅₄ absorbances. Observance of the same tendency for the original NOM from Lake Hohloh indicates that these XAD-fractions still having complex compound mixtures. However, the larger molecular weight fractions of the FAs showed higher preferential adsorptions onto TiO₂, which caused their faster degradation rates. Furthermore, FAs showed a greater reduction of the total THM formation potential (TTHMFP) and the organic halogen compounds adsorbable on activated carbon formation potential (AOXFP), in comparison with the HAs.