Christian Grøn

Characterization of the dissolved organic carbon in landfill leachate-polluted groundwater

Abstract Samples of dissolved organic carbon (DOC) were obtained from landfill leachate-polluted groundwater at Vejen Landfill, Denmark. The humic acids, fulvic acids and the hydrophilic fraction were isolated and purified. Based on DOC measurements, the fulvic acid fraction predominated, accounting for about 60% of the total amount of DOC with an apparent molecular weight of about 1800 Da. The hydrophilic fraction constituted about 30% of the total amount of DOC with an apparent molecular weight of about 2100 Da, and the humic acid fraction made up about 10% of the total amount of DOC with an apparent molecular weight of about 2600 Da. The elemental compositions of the humic acids, fulvic acids and the hydrophilic fraction were in the ranges typical for humic substances from other origins. The O/C ratios for humic acids, fulvic acids and the hydrophilic fraction were similar in the leachate-polluted groundwater. For humic acids the O/C ratios were slightly higher than reported in the literature, indicating a high content of carboxylic groups, phenolic groups or carbohydrates. Acid-base titration indicated that, in the fulvic acids and the hydrophilic fraction, carboxylic acids were the dominating functional group, representing about 6 meq g −1 . The weakly acidic groups in fulvic acids and the hydrophilic fraction represented about 1 and 3 meq g −1 , respectively. The total acidity in fulvic acids and the hydrophilic fraction accounted for 48–57% of the O/C ratio. In the humic acids, carboxylic groups made up about 3 meq g −1 and the weakly acidic groups made up about 1.5 meq g −1 . The total acidity accounted for 29–32% of the O/C ratio. The characterization of DOC in leachate-polluted groundwater in terms of humic acids, fulvic acids and hydrophilic fraction showed that the hydrophilic fraction resembles, in many ways, humic and fulvic acids; thus, a distinction between the fractions may be related to the methods only and be of little practical value. The three fractions constituting the DOC content in a sample should all be considered when evaluating processes such as metal complexation and transport of metals and hydrophobic, organic contaminants.

An inter-laboratory trial of the unified BARGE bioaccessibility method for arsenic, cadmium and lead in soil

The Bioaccessibility Research Group of Europe (BARGE) has carried out an inter-laboratory trial of a proposed harmonised in vitro physiologically based ingestion bioaccessibility procedure for soils, called the Unified BARGE Method (UBM). The UBM includes an initial saliva phase and simulated stomach and intestine compartments. The trial involved the participation of seven laboratories (five European and two North American) providing bioaccessibility data for As (11 samples), Cd (9 samples) and Pb (13 samples) using soils with in vivo relative bioavailability data measured using a swine model. The results of the study were compared with benchmark criteria for assessing the suitability of the UBM to provide data for human health risk assessments. Mine waste and slag soils containing high concentrations of As caused problems of poor repeatability and reproducibility which were alleviated when the samples were run at lower soil to solution ratios. The study showed that the UBM met the benchmark criteria for both the stomach and stomach & intestine phase for As. For Cd, three out of four criteria were met for the stomach phase but only one for the stomach & intestine phase. For Pb two, out of four criteria were met for the stomach phase and none for the stomach & intestine phase. However, the study recommends tighter control of pH in the stomach phase extraction to improve between-laboratory variability, more reproducible in vivo validation data and that a follow up inter-laboratory trial should be carried out.

Terrestrial natural sources of trichloromethane (chloroform, CHCl3) - An overview

The widespread use of volatile chlorinatedcompounds like chloroform, trichloroethene andtetrachloroethene in industrialized societiescauses a large annual release of thesecompounds into the environment. Due to theirrole as a source for halogen radicals involvedin various catalytic atmospheric reactioncycles, including the regulation of thestratospheric and tropospheric ozone layers,these compounds also constitute a risk fordrinking water resources as they can betransported to the groundwater fromcontaminated field sites or even fromatmospheric deposition. Therefore,identification and investigation of sources andsinks of volatile chlorinated compounds are ofparticular interest. Chloroform, a majorcontributor to natural gaseous chlorine, wasfound to be emitted by several anthropogenicand natural sources including the oceans andterrestrial areas. The origin of chloroform inthe terrestrial environment can beanthropogenic point sources, atmosphericdeposition, release by vegetation andproduction directly in the soil. The calculatedannual biogenic global chloroform emission is700 Gg, and marine and terrestrial environmentsare nearly equal contributors. The estimatedemissions from anthropogenic sources accountfor less than 10% of the estimated totalemissions from all sources. Among terrestrialsources, forests have recently been identifiedas contributing to the release of chloroform intothe environment. With the data available,annual emissions of chloroform to theatmosphere from forest sites were calculatedand compared to other natural sources. Atpresent knowledge, forests are only a minorsource in the total biogenic flux ofchloroform, contributing less than 1% to theannual global atmospheric input. However, itshould be noted that data are available forNorthern temperate forests only. The largetropical forest areas may provide a yet unknowninput of chloroform.

Haloperoxidase-like activity in spruce forest soil — a source of volatile halogenated organic compounds?

Abstract Haloperoxidase-15:e activity was monitored in samples from a podzol soil in an uncontaminated spruce forest at Klosterhede, Denmark. Activity for the oxidation of chloride and bromide was found. The pH optima for chlorination and brontination ranged between pH 2.5 and 4. Very high activity, up to 4.4 ∗ 10 3 mU kg −1 soil and 6.8 ∗ 10 3 mU kg −1 soil, respectively, was found in the surface layer. In the deeper soil layers, lower activity, between 1.5 – 23 mU kg −1 soil, was detected.

Formation of chloroform in spruce forest soil : results from laboratory incubation studies

The release of chloroform, 1,1,1-trichloroethane, tetrachloromethane, trichloroethene and tetrachloroethene from an organic rich spruce forest soil was studied in laboratory incubation experiments by dynamic headspace analysis, thermodesorption and gas chromatography. Performance parameters are presented for the dynamic headspace system. For spruce forest soil, the results showed a significant increase in chloroform concentration in the headspace under aerobic conditions over a period of seven days, whereas the concentration of the other compounds remained fairly constant. A biogenic formation of chloroform is suggested, whereas for the other compounds anthropogenic sources are assumed. The addition of trichloroacetic acid to the soil increased the release of chloroform from the soil. It is, therefore, suggested that trichloroacetic acid also contributed to the formation of chloroform. Under the experimental conditions, the spruce forest soil released chloroform concentrations corresponding to a rate of 12 microg m(-2) day(-1). Data on chloroform production rates are presented and compared with literature results, and possible formation mechanisms for chloroform are discussed.

Origin and structures of groundwater humic substances from three Danish aquifers

Structural, chemical, and isotopic parameters were used to identify the origins of groundwater humic substances from three Danish aquifers. A variety of analytical techniques (visible light absorption, molecular weight distribution, 13C-NMR spectroscopy, elemental composition with major elements and halogens, hydrolyzable amino acids and carbohydrates, carbon isotopes) applied to aquatic humic and fulvic acids led to consistent structural interpretations for each of the three aquifers studied. For humic substances in two aquifers, the analyses suggested source rocks in agreement with geological and hydrogeochemical information. In a third aquifer, source rock identification was inconclusive, and multiple fossil and recent organic carbon sources are suggested.

Particle-facilitated pesticide leaching from differently structured soil monoliths.

The leaching of soil particles and surface applied 14C-labeled glyphosate and pendimethalin from intact soil columns (height: 50 cm; diameter: 30 cm) were investigated, and the relative significance of particle-facilitated pesticide transport was quantified. Investigations were performed with a recently plowed (four columns) and an untilled (five columns) sandy loam soil. Leaching was driven by three irrigation events (15 mm h(-1); 2 h each). Samples of the leachate were filtered immediately (within 1.5 minutes) using 20 nm filters, and the 14C-pesticide content was determined for filtered and unfiltered samples. Pesticide leaching was driven by preferential water flow in macropores. For the plowed structure, 68+/-10% of the leached glyphosate (average of 6 events+/-std.) was bound to particles whereas significantly less glyphosate was bound to particles in leachate from minimally disturbed columns (17+/-12%). Thus, the results suggest that soil structure affected the mode of transport of glyphosate. It is likely that glyphosate sorbed strongly when applied on recently plowed soil (Kd=503 L kg(-1) for the soil), and that it could be mobilized and transported independently of soil particles more easily when applied on the minimally disturbed soil covered in part with crop residues (Kd<1 L kg(-1) for straw). Significantly less amounts of soil particles were leached from minimally disturbed (119-247 mg) than from recently plowed (441-731 mg) columns. The significance of particle-facilitated pendimethalin leaching could not be accurately quantified due to disagreement between control measurements based on both 14C-activity and chemical analyses.

Bioaccessibility of PAH from Danish soils

A test method for the determination of PAH relative bioaccessibility from contaminated soils was implemented and validated for use in risk assessment of soils from contaminated sites meeting performance requirement set for evaluation against regulatory limits. Relative bioaccessibilities of soil benzo(a)pyrene obtained with the test were linearly correlated to relative bioavailability data obtained previously in in vivo investigations with experimental animals, but the relative bioaccessibilities were lower than the relative bioavailabilities. Tests of soil samples from 4 Danish sites contaminated with benzo(a)pyrene and dibenz(a,h)anthracene from different sources and with different ages demonstrated that using the bioaccessible concentrations in risk assessment instead of total concentrations would have produced lower risk classifications of the sites. An urgent requirement is demonstrated for an accepted and valid method for investigating the bioavailability of organic soil contaminants such as PAH and also for soil samples with accepted relative bioavailability data.

Chloroform in a pristine aquifer system: Toward an evidence of biogenic origin

Ambient air, soil air, and groundwater were monitored for volatile halogenated organic compounds in a pristine spruce forest at Klosterhede, Denmark. Although this location is remote from industrial areas and free of any point sources of either soil or groundwater contamination, several volatile chlorinated hydrocarbons were detected. The concentration profiles of chloroform indicated a formation of this compound in the soil. Low concentrations were found in ambient air (0.02 ng L−1), higher concentrations in the upper soil layers (9.6 ng L−1 at 0.75 m below the surface), and a decrease with increasing depth (down to 1.5 ng L−1 just above the groundwater table at 7.5 m below the surface). For the other identified chlorinated compounds the concentration profiles were different from those of chloroform and exhibited less systematic variation between ambient air and soil air and with increasing depth. In the phreatic groundwater, high concentrations (up to 1.6 μg L−1) of chloroform and low concentrations (<0.01 μg L−1) of the other chlorinated compounds identified in air were found. Of the seven volatile brominated and iodinated compounds analyzed in ambient air, soil air, and groundwater, only bromoform was found and only in the upper soil layer. For chloroform a formation in the spruce forest soil is suggested, leading to concentrations in the groundwater in the micrograms per liter range.

Organic Halogens in Landfill Leachates

Using a group parameter, totalorganic halogens (TOX), high TOX concentrationswere found in leachates and leachate contaminatedgroundwaters at two Danish mixed sanitary andhazardous waste sites. With commonly used screeningprocedures for organic contaminants, the individualhalogenated organic compounds behind the high TOXcould not be found. Conversely, part of the TOX couldbe attributed to halogenated humic substances that cannot be analysed with conventional organic contaminantanalyses. Even though TOX can still be considered anindicator of leachate contamination in the aquifers,attempts to identify the halogenated contaminantsbehind the TOX using screening methods such as GC-MSwill be unsuccessful in most cases.