Kevin A. Thorn

Isolation of hydrophilic organic acids from water using nonionic macroporous resins

Abstract A method has been developed for the isolation of hydrophilic organic acids from aquatic environments using Amberlite ∗ XAD-4 resin. The method uses a two column array of XAD-8 and XAD-4 resins in series. The hydrophobic organic acids, composed primarily of aquatic fulvic acid, are removed from the sample on XAD-8, followed by the isolation of the more hydrophilic organic acids on XAD-4. For samples from a number of diverse environments, more of the dissolved organic carbon was isolated on the XAD-8 resin (23–58%) than on the XAD-4 resin (7–25%). For these samples, the hydrophilic acids have lower carbon and hydrogen contents, higher oxygen and nitrogen contents, and are lower in molecular weight than the corresponding fulvic acids. 13 C NMR analyses indicate that the hydrophilic acids have a lower concentration of aromatic carbon and greater heteroaliphatic, ketone and carboxyl content than the fulvic acid.

Chemical and optical changes in freshwater dissolved organic matter exposed to solar radiation

We studied the chemical and optical changes inthe dissolved organic matter (DOM) from twofreshwater lakes and a Sphagnum bog afterexposure to solar radiation. Stable carbonisotopes and solid-state 13C-NMR spectraof DOM were used together with optical andchemical data to interpret results fromexperimental exposures of DOM to sunlight andfrom seasonal observations of two lakes innortheastern Pennsylvania. Solar photochemicaloxidation of humic-rich bog DOM to smaller LMWcompounds and to DIC was inferred from lossesof UV absorbance, optical indices of molecularweight and changes in DOM chemistry. Experimentally, we observed a 1.2‰ enrichment in δ13

Crude oil in a shallow sand and gravel aquifer-II. Organic geochemistry

C and a 47% loss in aromaticC functionality in bog DOM samples exposed tosolar UVR. Similar results were observed inthe surface waters of both lakes. In latesummer hypolimnetic water in humic LakeLacawac, we observed 3 to 4.5‰enrichments in δ13C and a 30% increase inaromatic C relative to early spring valuesduring spring mixing. These changes coincidedwith increases in molecular weight and UVabsorbance. Anaerobic conditions of thehypolimnion in Lake Lacawac suggest thatmicrobial metabolism may be turning overallochthonous C introduced during springmixing, as well as autochthonous C. Thismetabolic activity produces HMW DOM during thesummer, which is photochemically labile andisotopically distinct from allochthonous DOM orautochthonous DOM. These results suggest bothphotooxidation of allochthonous DOM in theepilimnion and autotrophic production of DOM bybacteria in the hypolimnion cause seasonaltrends in the UV absorbance of lakes.

Identification of persistent anionic surfactant-derived chemicals in sewage effluent and groundwater

Abstract Crude oil spilled from a pipeline break in a remote area of north-central Minnesota has contaminated a shallow glacial outwash aquifer. Part of the oil was sprayed over a large area to the west of the pipeline and part of it accumulated in an oil body that floats at the water table to the east of the point of discharge. Total dissolved organic carbon (TDOC) concentrations in shallow groundwater collected in the oil spray area reach 16 mg/l. This is nearly an order of magnitude higher than the TDOC concentrations of native groundwater (∼2–3mg/l). The additional TDOC derives from the partial degradation of petroleum residues deposited at the land surface and transported to the aquifer by vertical recharge. In the vicinity of the oil body, TDOC concentrations in groundwater are 48 mg/l, 58% of the TDOC being composed of non-volatile organic C. The majority of the volatile DOC (63%) is a mixture of low-molecular-weight saturated, aromatic and alicyclic hydrocarbons derived from the oil. Downgradient from the oil body along the direction of groundwater flow, concentrations of all measured constituents of the TDOC pool decrease. Concentrations begin to decline most rapidly, however, in the zone where dissolved O 2 concentrations begin to increase, ∼50m downgradient from the leading edge of the oil. Within the anoxic zone near the oil body, removal rates of isometric monoaromatic hydrocarbons vary widely. This indicates that the removal processes are mediated mainly by microbiological activity. Molecular and spectroscopic characterization of the TDOC and its spatial and temporal variation provide evidence of the importance of biogeochemical processes in attenuating petroleum contaminants in this perturbed subsurface environment.

Ultraviolet irradiation effects incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter.

Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3–10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F300-50 groundwater have a minimum residence time in the range of 2.7–4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50–500 half lives.

Methylation patterns of aquatic humic substances determined by13C NMR spectroscopy

One of the concerns regarding the safety and efficacy of ultraviolet radiation for treatment of drinking water and wastewater is the fate of nitrate, particularly its photolysis to nitrite. In this study, N NMR was used to establish for the first time that UV irradiation effects the incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter (NOM). Irradiation of (15)N-labeled nitrate in aqueous solution with an unfiltered medium pressure mercury lamp resulted in the incorporation of nitrogen into Suwannee River NOM (SRNOM) via nitrosation and other reactions over a range of pH from approximately 3.2 to 8.0, both in the presence and absence of bicarbonate, confirming photonitrosation of the NOM. The major forms of the incorporated label include nitrosophenol, oxime/nitro, pyridine, nitrile, and amide nitrogens. Natural organic matter also catalyzed the reduction of nitrate to ammonia on irradiation. The nitrosophenol and oxime/nitro nitrogens were found to be susceptible to photodegradation on further irradiation when nitrate was removed from the system. At pH 7.5, unfiltered irradiation resulted in the incorporation of (15)N-labeled nitrite into SRNOM in the form of amide, nitrile, and pyridine nitrogen. In the presence of bicarbonate at pH 7.4, Pyrex filtered (cutoff below 290-300 nm) irradiation also effected incorporation of nitrite into SRNOM as amide nitrogen. We speculate that nitrosation of NOM from the UV irradiation of nitrate also leads to production of nitrogen gas and nitrous oxide, a process that may be termed photo-chemodenitrification. Irradiation of SRNOM alone resulted in transformation or loss of naturally abundant heterocyclic nitrogens.

Structural characteristics of the IHSS Suwannee River fulvic and humic acids determined by solution state C-13 NMR spectroscopy

13C NMR spectroscopy is used to examine the hydroxyl group functionality of a series of humic and fulvic acids from different aquatic environments. Samples first are methylated with13C-labeled diazomethane. The NMR spectra of the diazomethylated samples allow one to distinguish between methyl esters of car☐ylic acids, methyl ethers of phenolic hydroxyls, and methyl ethers of phenolic hydroxyls adjacent to two substituents. Samples are then permethylated with13C-labeled methyl iodide/NaH.13C NMR spectra of permethylated samples show that a significant fraction of the hydroxyl groups is not methylated with diazomethane alone. In these spectra methyl ethers of carbohydrate and aliphatic hydroxyls overlap with methyl ethers of phenolic hydroxyls. Side reactions of the methyltion procedure including carbon methylation in the CH3I/NaH procedure, are also examined. Humic and fulvic acids from bog, swamp, groundwater, and lake waters showssome differences in their distribution of hydroxyl groups, mainly in the concentrations of phenolic hydroxyls, which may be attributed to their different biogeochemical origins.

Characterization of humic acid fractions by C-13 nuclear magnetic resonance spectroscopy

Abstract The IHSS Suwannee River fulvic and humic acids have been examined by solution state C-13 NMR spectroscopy. C-13 NMR spectra acquired under quantitative conditions indicated proportions of sp hybridized carbons of 60 and 72 percent for the fulvic and humic acids, respectively. Attached Proton Test (APT) experiments clearly resolved the C-13 NMR spectra of both samples into methyl (0–26 ppm), methylene (26–43 ppm), methine (43–62 ppm and 62–92 ppm), protonated aromatic (105–135 ppm) and non-protonated aromatic (135–165 ppm) carbons. The APT spectra also revealed that the aliphatic moieties of the fulvic and humic acids are predominated by branched chain structures.

Crude Oil Metabolites in Groundwater at Two Spill Sites

Abstract Soil humic acids from different environments were fractionated by adsorption chromatography on Sephadex and characterized by C‐13 nuclear magnetic resonance (NMR) spectroscopy. The C‐13 NMR spectra of the fractions consist of some sharp, well‐resolved lines and some broad bands in contrast to the spectra of the unfractionated humic acids, where the bands are broader and less well‐resolved. The marked increase in resolution is apparently due to increased homogeneity of the fractions. These spectra are compared to the spectra of model compounds.

The use of variable temperature and magic-angle sample spinning in studies of fulvic acids

Two groundwater plumes in north central Minnesota with residual crude oil sources have 20 to 50 mg/L of nonvolatile dissolved organic carbon (NVDOC). These values are over 10 times higher than benzene and two to three times higher than Diesel Range Organics in the same wells. On the basis of previous work, most of the NVDOC consists of partial transformation products from the crude oil. Monitoring data from 1988 to 2015 at one of the sites located near Bemidji, MN show that the plume of metabolites is expanding toward a lakeshore located 335 m from the source zone. Other mass balance studies of the site have demonstrated that the plume expansion is driven by the combined effect of continued presence of the residual crude oil source and depletion of the electron accepting capacity of solid phase iron oxide and hydroxides on the aquifer sediments. These plumes of metabolites are not covered by regulatory monitoring and reporting requirements in Minnesota and other states. Yet, a review of toxicology studies indicates that polar metabolites of crude oil may pose a risk to aquatic and mammalian species. Together the results suggest that at sites where residual sources are present, monitoring of NVDOC may be warranted to evaluate the fates of plumes of hydrocarbon transformation products.