Evaluating peats for their capacities to remove odorous compounds from liquid swine manure using headspace “solid‐phase microextraction”

Abstract

This paper reports on research designed to investigate the capacities of different highly characterized peats to remove odorous compounds from liquid swine manure (LSM). Peat types representing a wide range of properties were tested in order to establish which chemical and physical properties might be most indicative of their capacities to remediate odors produced by LSM. Eight percent slurries (of peat/LSM) were measured for odor changes after 24 hours using odor panel and GC/MS‐Solid‐phase microextraction (GC/MS‐SPME) analysis.

The GC/MS‐SPME and odor panel results indicated that, although all peats tested in this study were found to be effective at removing odor‐causing compounds found in LSM, some peats tended to work better than others. Overall, the peats that were the most effective at removing odor‐causing compounds tended to have lower bulk densities, ash contents, fulvic acids contents, and guaiacyl lignins contents,and higher water holding capacities, hydraulic conductivities, “total other lignins”; contents, hydrogen contents, carbon contents, and total cellulose contents.

GC/MS‐SPME analysis was found to be a reasonably inexpensive and efficient way of conducting this type of research. It allows one to identify a large number of the odor‐causing compounds found in LSM, and more importantly, to detect with some precision specific differences in the amounts of these compounds between peat types.     

Retention of nitrogen and phosphorous from liquid swine and poultry manures using highly characterized peats

This paper reports on research designed to test the hypothesis that differences in peat composition will cause differences in amounts of N and P retained during contact with liquid swine manure (LSM) and liquid poultry manure (LPM). Peat types representing a wide range of properties were tested in order to establish which chemical and physical properties might be most indicative of their capacities to retain N and P from LSM and LPM. Eight-percent slurries (peat/LSM and peat/LPM) were measured for total nitrogen (TKN) and total phosphorous (TP) after 6, 24 and 96 hours. Tests were done to determine the TKN and TP contents of these peats, the LSM, and the LPM, both before and after they were mixed together. The N and P retention results revealed that most peats worked reasonably well at retaining N and P from either LSM or LPM. However, some peats were more effective than others. These peats also decreased the N and P levels in the liquid portion of the LSM. Peats with higher N retention capacities tended to have lower ash contents, but higher macroporosities and total cellulose contents. Peats with higher P retention capacities tended to have lower bulk densities, ash contents, total guaiacyl lignins contents, fulvic acids contents, but higher microporosities, macroporosities, H contents, and total cellulose contents. Peats with higher N and P retention capacities also had humic acid contents between 5-7%. The results of this study suggest that if these peats are used to reduce odors and N and P contamination, possible byproducts could be the production of odorless fertilizers.     

Role of protein, amino acids, and enzyme activity on odor production from anaerobically digested and dewatered biosolids.

The main objective of this research was to test the hypothesis that bioavailable protein and, more specifically, the sulfur-containing amino acids within the protein, can be degraded by proteolytic enzymes to produce odor-causing compounds--mainly volatile sulfur compounds (VSCs)--during biosolids storage. To achieve these objectives, samples of digester effluent and cake solids were collected at 11 different wastewater treatment plants in North America, and the samples were analyzed for protein and amino acid content and general protein-degrading enzyme activity. At the same time, cake samples were stored using headspace bottles, the concentration of VSCs were measured using gas chromatography, and olfactometry measurements were made by a trained odor panel. The results showed that the bound cake protein content and methionine content was well-correlated with VSC production and the detection threshold measured by the odor panel.     

Filters and Filter Media for the Cement Industry

To correlate the odor strength of natural gas with its sulfur analysis, the recognition odor thresholds of 18 sulfur compounds were determined using an untrained panel of 35 peopie. For each test a series of odor concentrations graduated in increments of 10^0.2 was presented to the panel in random order over a range of concentrations above and below the olfactory thresholds of all panelists. Each odor was tested on at least three different days. Desired odor concentrations were produced by dynamic blending of gaseous mixtures of the odorous compounds with air. All testing was done out-of-doors during clement weather when no ambient odors were apparent. The range of olfactory response was found to be much greater for certain compounds than for others. Branching of the hydro-carbon chain increased odor strength. Certain compounds appeared to evoke anomalous responses.     

Characterization of livestock odors using steel plates, solid-phase microextraction, and multidimensional gas chromatography-mass spectrometry-olfactometry

Livestock operations are associated with emissions of odor, gases, and particulate matter (PM). Livestock odor characterization is one of the most challenging analytical tasks. This is because odor-causing gases are often present at very low concentrations in a complex matrix of less important or irrelevant gases. The objective of this project was to develop a set of characteristic reference odors from a swine barn in Iowa and, in the process, identify compounds causing characteristic swine odor. Odor samples were collected using a novel sampling methodology consisting of clean steel plates exposed inside and around the swine barn for < or =1 week. Steel plates were then transported to the laboratory and stored in clean jars. Headspace solid-phase microextraction was used to extract characteristic odorants collected on the plates. All of the analyses were conducted on a gas chromatography-mass spectrometry-olfactometry system where the human nose is used as a detector simultaneously with chemical analysis via mass spectrometry. Multidimensional chromatography was used to isolate and identify chemicals with high-characteristic swine odor. The effects of sampling time, distance from a source, and the presence of PM on the abundance of specific gases, odor intensity, and odor character were tested. Steel plates were effectively able to collect key volatile compounds and odorants. The abundance of specific gases and odor was amplified when plates collected PM. The results of this research indicate that PM is major carrier of odor and several key swine odorants. Three odor panelists were consistent in identifying p-cresol as closely resembling characteristic swine odor, as well as attributing to p-cresol the largest odor response out of the samples. Further research is warranted to determine how the control of PM emissions from swine housing could affect odor emissions.     

Generation pattern of sulfur containing gases from anaerobically digested sludge cakes.

Eleven dewatered sludge cakes collected from anaerobic digesters at different treatment plants were evaluated for the amount, type, and pattern of odorous gas production. All but one of the sludge cakes were from mesophilic anaerobic digesters. One was from a thermophilic digester. The pattern and quantities of sulfur gases were found to be unique for each of the samples with regard to the products produced, magnitude, and subsequent decline. The main odor-causing chemicals were volatile sulfur compounds, which included hydrogen sulfide, methanethiol, and dimethyl sulfide. Volatile sulfur compound production peaked in 3 to 8 days and then declined. The decline was a result of conversion of organic sulfur compounds to sulfide. In one side-by-side test, a high-solids centrifuge cake generated more odorous compounds than the low-solids centrifuge cake. The data show that anaerobic digestion does not eliminate the odor potential of anaerobically digested dewatered cakes.     

Storage and distribution of trace metals and spheroidal carbonaceous particles (SCPs) from atmospheric deposition in the catchment peats of Lochnagar, Scotland.

Lochnagar is a remote mountain lake to the south-east of the Cairngorm region in Scotland. Its catchment receives anthropogenic trace metals solely from atmospheric deposition. Ten peat cores were taken from the catchment and analysis confirmed that they have been contaminated by trace metals. The peats have an high affinity for trace metals and this results in metal accumulation in the surface peat layers. The formation of trace metal sulphides may also reduce remobilisation. In this way, trace metals derived from atmospheric deposition have been scavenged and accumulated. In contaminated peat layers, 77.4% Hg, 89.6% Pb, 93.4% Cu, 72.4% Zn and 86.5% Cd of the total stored are from anthropogenic sources. The accumulated trace metals in the peats can potentially influence the lake system through erosion. Spheroidal carbonaceous particle (SCP) profiles were used to date the peat cores. By referring to the SCP profiles in the peats and comparing these with the trace metal profiles in the lake sediments, the mobility of trace metals in the catchment peats is confirmed.     

Wet scrubber analysis of volatile organic compound removal in the rendering industry

The promulgation of odor control rules, increasing public concerns, and U.S. Environmental Protection Agency (EPA) air regulations in nonattainment zones necessitates the remediation of a wide range of volatile organic compounds (VOCs) generated by the rendering industry. Currently, wet scrubbers with oxidizing chemicals are used to treat VOCs; however, little information is available on scrubber efficiency for many of the VOCs generated within the rendering process. Portable gas chromatography/mass spectrometry (GC/MS) units were used to rapidly identify key VOCs on-site in process streams at two poultry byproduct rendering plants. On-site analysis was found to be important, given the significant reduction in peak areas if samples were held for 24 hr before analysis. Major compounds consistently identified in the emissions from the plant included dimethyl disulfide, methanethiol, octane, hexanal, 2-methylbutanal, and 3-methylbutanal. The two branched aldehydes, 2-methylbutanal and 3-methylbutanal, were by far the most consistent, appearing in every sample and typically the largest fraction of the VOC mixture. A chlorinated hydrocarbon, methanesulfonyl chloride, was identified in the outlet of a high-intensity wet scrubber, and several VOCs and chlorinated compounds were identified in the scrubbing solution, but not on a consistent basis. Total VOC concentrations in noncondensable gas streams ranged from 4 to 91 ppmv. At the two plants, the odor-causing compound methanethiol ranged from 25 to 33% and 9.6% of the total VOCs (v/v). In one plant, wet scrubber analysis using chlorine dioxide (ClO2) as the oxidizing agent indicated that close to 100% of the methanethiol was removed from the gas phase, but removal efficiencies ranged from 20 to 80% for the aldehydes and hydrocarbons and from 23 to 64% for total VOCs. In the second plant, conversion efficiencies were much lower in a packed-bed wet scrubber, with a measurable removal of only dimethyl sulfide (20-100%).     

Characterization of odor released during handling of swine slurry: Part I. Relationship between odorants and perceived odor concentrations

Odor emission from livestock production systems is a major nuisance in many rural areas. This study aimed at determining the major airborne chemical compounds responsible for the unpleasant odor perceived in swine facilities during slurry handling, and at proposing predictive models of odor concentration (OC) based on the concentrations of specific odorants in the air. A multivariate data analysis strategy involving principal components analysis and multiple linear regressions was implemented to analyze the relationships between concentration of 35 gases (measured by GC/MS or gas detection tubes), and the overall OC perceived by sensory analysis. The study compiled data on the concentration of odor and odorants, measured in the headspace of 24 unstored and stored slurry samples collected from three different types of production units on 8 commercial swine farms. Among all the measured constituents, OC was found to have the highest correlation with the sulfur containing compounds (i.e. hydrogen sulfide, dimethylsulfide, dimethyldisulfide, dimethyltrisulfide). The concentration of hydrogen sulfide accounted for 68% of the variation in OC above the stirred slurry samples. The highest concentrations of volatile organic compounds were observed for phenols and indoles, which made a significant contribution to the overall OC when the slurry was fresh. The contribution of ammonia to the OC was only significant in the absence of hydrogen sulfide. The precision of predictive models of OC based on the concentration of specific odorants in the air was satisfactory (R² between 0.66 and 0.89). Hence, this study suggests that monitoring of specific odor compounds released from agitated swine slurry can be used to predict the concentration of odor perceived close to the source (e.g. at storage units), allowing the assessment of odor nuisance potentials.     

Treatment of odor by a seashell biofilter at a wastewater treatment plant

Biofilters are becoming an increasingly popular treatment device for odors and other volatiles found at wastewater treatment plants. A seashell media based biofilter was installed in April 2011 at Lake Wildwood Wastewater Treatment Plant located in Penn Valley, California. It was sampled seasonally to examine its ability to treat odorous compounds found in the air above the anaerobic equalization basin at the front end of the plant and to examine the properties of the biofilter and its recirculating water system. The odor profile method sensory panels found mainly sulfide odors (rotten eggs and rotten vegetable) and some fecal odors. This proved to be a useful guidance tool for selecting the required types of chemical sampling. The predominant odorous compounds found were hydrogen sulfide, methyl mercaptan and dimethyl sulfide. These compounds were effectively removed by the biofilter at greater than 99% removal efficiency therein reducing the chemical concentrations to below their odor thresholds. Aldehydes found in the biofilter were below odor thresholds but served as indicators of biological activity. Gas chromatography with mass spectrometry and gas chromatography with sensory detection showed the presence of dimethyl disulfide and dimethyl trisulfide as well, but barely above their respective odor thresholds. The neutrality of the pH of the recirculating water was variable depending on conditions in the biofilter, but a local neutral pH was found in the shells themselves. Other measurements of the recirculating water indicated that the majority of the bio-activity takes place in the first stage of the biofilter. All measurements performed suggest that this seashell biofilter is successful at removing odors found at Lake Wildwood. This study is an initial examination into the mechanism of the removal of odorous compounds in a seashell biofilter.

Implications:?This paper presents a thorough examination of a seashell media biofilter, a sustainable treatment technology used to remove reduced sulfide compounds. The durable performance of the seashell biofilter ensures that odors will be adequately controlled, preventing odor nuisance to surrounding residences, which is an emerging problem faced by waste management facilities. The odor profile method technique used in this study can be applied in many situations by waste management facilities and regulatory air management organizations for source tracking in relation to prevention and management of odor complaints, respectively.     

Wet Scrubber Analysis of Volatile Organic Compound Removal in the Rendering Industry

Abstract

The promulgation of odor control rules, increasing public concerns, and U.S. Environmental Protection Agency (EPA) air regulations in nonattainment zones necessitates the remediation of a wide range of volatile organic compounds (VOCs) generated by the rendering industry. Currently, wet scrubbers with oxidizing chemicals are used to treat VOCs; however, little information is available on scrubber efficiency for many of the VOCs generated within the rendering process. Portable gas chromatography/mass spectrometry (GC/MS) units were used to rapidly identify key VOCs on-site in process streams at two poultry byproduct rendering plants. On-site analysis was found to be important, given the significant reduction in peak areas if samples were held for 24 hr before analysis. Major compounds consistently identified in the emissions from the plant included dimethyl disulfide, methanethiol, octane, hexanal, 2-methylbutanal, and 3-methylbutanal. The two branched aldehydes, 2-methylbutanal and 3-methylbutanal, were by far the most consistent, appearing in every sample and typically the largest fraction of the VOC mixture.

A chlorinated hydrocarbon, methanesulfonyl chloride, was identified in the outlet of a high-intensity wet scrubber, and several VOCs and chlorinated compounds were identified in the scrubbing solution, but not on a consistent basis. Total VOC concentrations in noncondensable gas streams ranged from 4 to 91 ppmv. At the two plants, the odor-causing compound methanethiol ranged from 25 to 33% and 9.6% of the total VOCs (v/v). In one plant, wet scrubber analysis using chlorine dioxide (ClO2) as the oxidizing agent indicated that close to 100% of the methanethiol was removed from the gas phase, but removal efficiencies ranged from 20 to 80% for the aldehydes and hydrocarbons and from 23 to 64% for total VOCs. In the second plant, conversion efficiencies were much lower in a packed-bed wet scrubber, with a measurable removal of only dimethyl sulfide (20–100%).     

Odors and volatile organic compounds released from ventilation filters

Used supply air filters were studied by sensory and chemical methods. In addition, filter dust was examined by thermodesorption/cold trap (TCT) and headspace (HS) devices connected to a GC–MS. The prefilter was the main odor source in the ventilation unit, but when humidifier was turned on odor was released mainly from the fine filter. However, the effect of the relative humidity (RH) was only temporary. At the same time, there was an increase in the concentration of aldehydes after the filters. Aldehydes, carboxylic acids, and nitrogen-containing organic compounds were the main emission products in the thermodesorption analyses of the filter dust. Many of these compounds have low odor threshold values and, therefore, contribute to the odor released from the filters. Especially, the role of aldehydes seems to be important in the odor formation.     

Comparison of seasonal phenol and p-cresol emissions from ground-level area sources in a dairy operation in central Texas

Although there are more than 200 odor-causing volatile organic compounds (VOCs), phenol and p-cresol are two prominent odor-causing VOCs found downwind from concentrated animal feeding operations (CAFOs). The VOC emissions from cattle and dairy production are difficult to quantify accurately because of their low concentrations, spatial variability, and limitations of available instruments. To quantify VOCs, a protocol following US. Environmental Protection Agency (EPA) Method TO-14A has been established based on the isolation flux chamber method and a portable gas chromatograph (GC) coupled with a purge-and-trap system. The general objective of this research was to quantify phenol and p-cresol emission rates (ERs) from different ground-level area sources (GLASs) in a free-stall dairy during summer and winter seasons using this protocol. Two-week-long sampling campaigns were conducted in a dairy operation in central Texas. Twenty-nine air samples were collected during winter and 37 samples were collected during summer from six specifically delineated GLASs (barn, loafing pen, lagoon, settling basin, silage pile, and walkway) at the free-stall dairy. Thirteen VOCs were identified during the sampling period and the GC was calibrated for phenol and p-cresol, the primary odorous VOCs identified. The overall calculated ERs for phenol and p-cresol were 2656 +/- 728 and 763 +/- 212 mg hd(-1) day(-1), respectively, during winter. Overall phenol and p-cresol ERs were calculated to be 1183 +/- 361 and 551 +/- 214 mg hd(-1) day(-1), respectively, during summer. In general, overall phenol and p-cresol ERs during winter were about 2.3 and 1.4 times, respectively, higher than those during summer.     

Adsorption of phenolic compounds from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent

A water-compatible hypercrosslinked polymeric adsorbent (NJ-8) for adsorbing and removing phenolic compounds from their aqueous solutions was prepared. This product can be used directly without a wetting process. Its adsorption property toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was tested using the commercial Amberlite XAD-4 as a reference. The capacities of equilibrium adsorption for all four phenolic compounds on the NJ-8 from their aqueous solutions are around two times as high as that of Amberlite XAD4 within the temperature range 283-323 K, which may contribute to their micropore structure and the partial polarity on the network. Freundlich isotherm equations, as well as relative adsorption capacities and isosteric adsorption enthalpies for the four phenolic compounds, indicate that the adsorption of phenolic compounds on the NJ-8 resin is a physical adsorption process. Mini-column adsorption studies for phenol on Amberlite XAD4 and NJ-8 resins show that the breakthrough adsorption capacities are 0.54 and 0.99 mmol/ml, and the total capacities are 0.62 and 1.37 mmol/ml, while no extra acetone was needed to remove the adsorbed phenol from NJ-8 as from Amberlite XAD4.     

Potentially toxic metals in ombrotrophic peat along a 400 km English-Scottish transect

Four samples of ombrotrophic peat were collected from each of 10 upland locations in a transect from the southern Pennines to the Highland Boundary Fault, a total distance of ca. 400 km. Bulk compositions and other properties were determined. Total contents of Al and heavy metals (Ni, Cu, Zn, Cd, Pb) were determined following digestion with hydrofluoric acid, and concentrations of metals extractable with dilute nitric acid were also measured. Supernatants obtained from aqueous extractions of the peat samples were analysed for pH, major cations and anions, dissolved organic carbon and dissolved metals, and concentrations of free metal ions (Al(3+), Ni(2+), etc.) were estimated by applying a chemical speciation model. Both total and HNO(3)-extractable metal concentrations varied along the transect, the highest values being found at locations close to industrial and former mining areas. The HNO(3)-extractable soil metal contents of Ni, Cu and Cd were appreciably lower than lowest-observed-effect-concentrations (LOEC) for toxicity towards microorganisms in acid, organic rich soils. However, the contents of Zn at two locations, and of Pb at five locations exceeded LOECs, suggesting that they may be exerting toxic effects in the peats. Soil solution concentrations of free heavy metal ions (Cu(2+), Zn(2+), Cd(2+), Pb(2+)) were substantially lower than LOECs for toxicity towards vascular plants, whereas concentrations of Al(3+) were near to toxic levels at two locations.     

Characterization of incense smoke by solid phase microextraction—Comprehensive two-dimensional gas chromatography (GC×GC)

Comprehensive two-dimensional gas chromatography in tandem with flame ionization detection (GC×GC-FID) was used for the qualitative fingerprint characterisation of four different types of powdered incense headspace (H/S), and incense smoke. Volatile organic compounds (VOCs) in the incense powder and smoke were extracted by using solid phase microextraction (SPME) with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) 65 μm fiber. Low-polarity/polar, and polar/non-polar phase combinations were tested to contrast the GC×GC separation of components in these two column sets.A total of 324 compounds were tentatively identified, with more than 100 compounds in incense powders and more than 200 compounds in the incense smoke, by using GC coupled to quadrupole mass spectrometric detection. Identification required at least 90% match with the NIST library; otherwise they were considered as unidentified. The smoke stream comprised compounds originating from the incense powder, and combustion products such as PAH, N-heterocyclics, and furans. However, GC×GC was able to separate many more volatile compounds (possibly hundreds more) present in the complex smoke samples, many of which cannot be separated by conventional 1D-GC; this is a direct consequence of the high-resolution power of GC×GC. GC×GC fingerprint comparison of powder H/S with smoke allows facile subtraction of the former from the latter to assist identification of compounds generated from burning incense.     

Dispersion modeling to compare alternative technologies for odor remediation at swine facilities

The effectiveness of 18 alternative technologies for reducing odor dispersion at and beyond the boundary of swine facilities was assessed in conjunction with an initiative sponsored through agreements between the Attorney General of North Carolina and Smithfield Foods, Premium Standard Farms, and Frontline Farmers. The trajectory and spatial distribution of odor emitted at each facility were modeled at 200 and 400 m downwind from each site under two meteorological conditions (daytime and nighttime) using a Eulerian-Lagrangian model. To predict the dispersion of odor downwind, the geographical area containing the odorant sources at each facility was partitioned into 10-m2 grids on the basis of satellite photographs and architectural drawings. Relative odorant concentrations were assigned to each grid point on the basis of intensity measurements made by the trained odor panel at each facility using a 9-point rating scale. The results of the modeling indicated that odor did not extend significantly beyond 400 m downwind of any of the test sites during the daytime when the layer of air above the earth's surface is usually turbulent. However, modeling indicated that odor from all full-scale farms extended beyond 400 m onto neighboring property in the evenings when deep surface cooling through long-wave radiation to space produces a stable (nocturnal) boundary layer. The results also indicated that swine housing, independent of waste management type, plays a significant role in odor downwind, as do odor sources of moderate to moderately high intensity that emanate from a large surface area such as a lagoon. Human odor assessments were utilized for modeling rather than instrument measurements of volatile organic compounds (VOCs), hydrogen sulfide, ammonia, or particulates less than 10 microm in diameter (PM10) because these physical measurements obtained simultaneously with human panel ratings were not found to accurately predict human odor intensity in the field.     

Review of Federally Sponsored Research on Diesel Exhaust Odors

The information presented in this paper is directed to persons concerned with control of exhaust odors from diesel-engine-powered vehicles. This paper summarizes projects sponsored by the Environmental Protection Agency (EPA) over the past years in the field of diesel-exhaust odor. These investigations have concentrated on developing measurement methods for quantifying different odor levels, evaluating various odor control methods, and evaluating public opinions of such odors.

A human panel method using odor reference standards has been found suitable to measure these odor levels. In addition to this technique, chemical characterization work has been sponsored under a project jointly sponsored by the Coordinating Research Council and the EPA to isolate and identify those species responsible for the odor.

Knowledge of these odorous compounds and the techniques necessary to isolate them should lead to development of a chemical method to measure this type of odor, in place of human panelists. Such basic information would also lead to developing control techniques to minimize this odor.

Several control techniques were evaluated for diesel exhaust odor. To date, the most effective method is an improved needle injector for use in the Detroit Diesel type E 6V-71 engine commonly used in buses.

Finally, public reaction to diesel-engine-exhaust odor has been measured. It has been found that a systematic relationship exists between increasing public objections and increasing diesel odor intensity.     

Long-term effects of amendment with liquid swine manure on proton binding behavior of soil humic substances

The acid-base properties of humic acids (HAs) and fulvic acids (FAs) isolated from liquid swine manure (LSM), soils amended with either 90 or 150 m(3)ha(-1)year(-1) of LSM for 7 years, and the corresponding unamended control soil were investigated by a current potentiometric titration method. The non-ideal competitive adsorption (NICA)-Donnan model for proton binding by two classes of binding sites (i.e., carboxylic- and phenolic-type groups) was fit to titration data, and a set of fitting parameters was obtained for each HA and FA sample. The NICA-Donnan model was shown to describe with a great degree of accuracy the behavior of experimental titration datasets, and highlighted important differences in the acid-base properties of the HAs and FAs examined. When compared to the unamended soil HA and FA, LSM-HA and LSM-FA, had smaller acidic functional group contents, larger proton binding affinities of both carboxylic- and phenolic-type groups, smaller heterogeneity of carboxylic-type groups, and smaller, in the case of HA, or similar, in the case of FA, heterogeneity of phenolic-type groups. Amendment with LSM caused a decrease of acidic functional group contents and a slight increase of proton binding affinities of carboxylic- and phenolic-type groups of soil HAs and FAs. Further, LSM application induced a decrease of the heterogeneity of carboxylic-type groups, whereas appeared not to affect substantially the heterogeneity of phenolic-type groups of LSM-amended soil HAs and FAs. These effects were more evident for HAs than for FAs and tended to slightly increase with increasing LSM amendment rate.