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Characterization and disinfection by-product formation potential of natural organic matter in surface and ground waters from Northern Florida

Streamwaters in northern Florida have large concentrations of natural organic matter (NOM), and commonly flow directly into the ground water system through karst features, such as sinkholes. In this study NOM from northern Florida stream and ground waters was fractionated, the fractions characterized by infrared (IR) and nuclear magnetic resonance (NMR), and then chlorinated to investigate their disinfection by-product (DBP) formation potential (FP). As the NOM character changed (as quantified by changes in NOM distribution in various fractions, such as hydrophilic acids or hydrophobic neutrals) due to migration through the aquifer, the total organic halide (TOX)-FP and trihalomethane (THM)-FP yield of each of these fractions varied also. In surface waters, the greatest DBP yields were produced by the colloid fraction. In ground waters, DBP yield of the hydrophobic acid fraction (the greatest in terms of mass) decreased during infiltration.

Florida↗

Trihalomethanes formed from natural organic matter isolates: Using isotopic and compositional data to help understand sources

Over 20 million people drink water from the Sacramento-San Joaquin Delta despite problematic levels of natural organic matter (NOM) and bromide in Delta water, which can form trihalomethanes (THMs) during the treatment process. It is widely believed that NOM released from Delta peat islands is a substantial contributor to the pool of THM precursors present in Delta waters. Dissolved NOM was isolated from samples collected at five channel sites within the Sacramento-San Joaquin Rivers and Delta, California, USA, and from a peat island agricultural drain. To help understand the sources of THM precursors, samples were analyzed to determine their chemical and isotopic composition, their propensity to form THMs, and the isotopic composition of the THMs. The chemical composition of the isolates was quite variable, as indicated by significant differences in carbon-13 nuclear magnetic resonance spectra and carbon-to-nitrogen concentration ratios. The lowest propensity to form THMs per unit of dissolved organic carbon was observed in the peat island agricultural drain isolate, even though it possessed the highest fraction of aromatic material and the highest specific ultraviolet absorbance. Changes in the chemical and isotopic composition of the isolates and the isotopic composition of the THMs suggest that the source of the THMs precursors was different between samples and between isolates. The pattern of variability in compositional and isotopic data for these samples was not consistent with simple mixing of river- and peat-derived organic material.

ACS Symposium Series↗

Redox chemistry and natural organic matter (NOM): Geochemists' dream, analytical chemists' nightmare

Natural organic matter (NOM) is an inherently complex mixture of polyfunctional organic molecules. Because of their universality and chemical reversibility, oxidation/reductions (redox) reactions of NOM have an especially interesting and important role in geochemistry. Variabilities in NOM composition and chemistry make studies of its redox chemistry particularly challenging, and details of NOM-mediated redox reactions are only partially understood. This is in large part due to the analytical difficulties associated with NOM characterization and the wide range of reagents and experimental systems used to study NOM redox reactions. This chapter provides a summary of the ongoing efforts to provide a coherent comprehension of aqueous redox chemistry involving NOM and of techniques for chemical characterization of NOM. It also describes some attempts to confirm the roles of different structural moieties in redox reactions. In addition, we discuss some of the operational parameters used to describe NOM redox capacities and redox states, and describe nomenclature of NOM redox chemistry. Several relatively facile experimental methods applicable to predictions of the NOM redox activity and redox states of NOM samples are discussed, with special attention to the proposed use of fluorescence spectroscopy to predict relevant redox characteristics of NOM samples.

ACS Symposium Series↗

Generation of ethylene tracer by noncatalytic pyrolysis of natural gas at elevated pressure

There is a critical need within the pipeline gas industry for an inexpensive and reliable technology to generate an identification tag or tracer that can be added to pipeline gas to identify gas that may escape and improve the deliverability and management of gas in underground storage fields. Ethylene is an ideal tracer, because it does not exist naturally in the pipeline gas, and because its physical properties are similar to the pipeline gas components. A pyrolysis process, known as the Tragen process, has been developed to continuously convert the ???2%-4% ethane component present in pipeline gas into ethylene at common pipeline pressures of 800 psi. In our studies of the Tragen process, pyrolysis without steam addition achieved a maximum ethylene yield of 28%-35% at a temperature range of 700-775 ??C, corresponding to an ethylene concentration of 4600-5800 ppm in the product gas. Coke deposition was determined to occur at a significant rate in the pyrolysis reactor without steam addition. The ?? 13C isotopic analysis of gas components showed a ?? 13C value of ethylene similar to ethane in the pipeline gas, indicating that most of the ethylene was generated from decomposition of the ethane in the raw gas. However, ?? 13C isotopic analysis of the deposited coke showed that coke was primarily produced from methane, rather than from ethane or other heavier hydrocarbons. No coke deposition was observed with the addition of steam at concentrations of > 20% by volume. The dilution with steam also improved the ethylene yield. ?? 2005 American Chemical Society.

Energy and Fuels↗

Adsorbed natural gas storage with activated carbons made from Illinois coals and scrap tires

Activated carbons for natural gas storage were produced from Illinois bituminous coals (IBC-102 and IBC-106) and scrap tires by physical activation with steam or CO 2 and by chemical activation with KOH, H 3 PO 4 , or ZnCl 2 . The products were characterized for N 2 -BET area, micropore volume, bulk density, pore size distribution, and volumetric methane storage capacity ( V m / V s ). V m / V s values for Illinois coal-derived carbons ranged from 54 to 83 cm 3 /cm 3 , which are 35−55% of a target value of 150 cm 3 /cm 3 . Both granular and pelletized carbons made with preoxidized Illinois coal gave higher micropore volumes and larger V m / V s values than those made without preoxidation. This confirmed that preoxidation is a desirable step in the production of carbons from caking materials. Pelletization of preoxidized IBC-106 coal, followed by steam activation, resulted in the highest V m / V s value. With roughly the same micropore volume, pelletization alone increased V m / V s of coal carbon by 10%. Tire-derived carbons had V m / V s values ranging from 44 to 53 cm 3 /cm 3 , lower than those of coal carbons due to their lower bulk densities. Pelletization of the tire carbons increased bulk density up to 160%. However, this increase was offset by a decrease in micropore volume of the pelletized materials, presumably due to the pellet binder. As a result, V m / V s values were about the same for granular and pelletized tire carbons. Compared with coal carbons, tire carbons had a higher percentage of mesopores and macropores.

Energy and Fuels↗

Influence of natural organic matter on the adsorption of metal ion onto clay particles

The influence of natural organic matter (NOM) on the adsorption of Al, Fe, Zn, and Pb onto clay minerals was investigated. Adsorption experiments were carried out at pH = 5 and pH = 7 in the presence and absence of NOM. In general, the presence of NOM decreased the adsorption of metal ions onto the clay particles. Al and Fe were strongly influenced by NOM, whereas Zn and Pb adsorption was only slightly altered. The interaction of the metal ions with the minerals and the influence of NOM on this interaction was investigated by coupling SdFFF with an inductively coupled plasma mass spectrometer (ICPMS) or an inductively coupled plasma atomic emission spectrometer (ICPAES). Quantitative atomization of the clay particles in the ICP was confirmed by comparing elemental content determined by direct injection of the clay into the ICPMS with values from acid digestion. Particle sizes of the clays were found to be between 0.1 and 1 μm by sedimentation field-flow fractionation (SdFFF) with UV detection. Aggregation of particles due to metal adsorption was observed using SdFFF-ICPMS measurements. This aggregation was dependent on the specific metal ion and decreased in the presence of NOM and at higher pH value.

Environmental Science & Technology↗

Atmospheric mercury deposition during the last 270 years: A glacial ice core record of natural and anthropogenic sources

Mercury (Hg) contamination of aquatic ecosystems and subsequent methylmercury bioaccumulation are significant environmental problems of global extent. At regional to global scales, the primary mechanism of Hg contamination is atmospheric Hg transport. Thus, a better understanding of the long-term history of atmospheric Hg cycling and quantification of the sources is critical for assessing the regional and global impact of anthropogenic Hg emissions. Ice cores collected from the Upper Fremont Glacier (UFG), Wyoming, contain a high-resolution record of total atmospheric Hg deposition (ca. 1720−1993). Total Hg in 97 ice-core samples was determined with trace-metal clean handling methods and low-level analytical procedures to reconstruct the first and most comprehensive atmospheric Hg deposition record of its kind yet available from North America. The record indicates major atmospheric releases of both natural and anthropogenic Hg from regional and global sources. Integrated over the past 270-year ice-core history, anthropogenic inputs contributed 52%, volcanic events 6%, and background sources 42%. More significantly, during the last 100 years, anthropogenic sources contributed 70% of the total Hg input. Unlike the 2−7-fold increase observed from preindustrial times (before 1840) to the mid-1980s in sediment-core records, the UFG record indicates a 20-fold increase for the same period. The sediment-core records, however, are in agreement with the last 10 years of this ice-core record, indicating declines in atmospheric Hg deposition.

Environmental Science & Technology↗

Use of ICP/MS with ultrasonic nebulizer for routine determination of uranium activity ratios in natural water

A method is described that allows precise determination of 234 U/ 238 U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (±0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (±0.25% RSD, 1 sigma) and alpha particle spectrometry (±5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 μg/L to nearly 100 μg/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.

Environmental Science & Technology↗

Influence of natural organic matter source on copper speciation as demonstrated by Cu binding to fish gills, by ion selective electrode, and by DGT gel sampler

Rainbow trout ( Oncorhynchus mykiss , 2 g) were exposed to 0−5 μM total copper in ion-poor water for 3 h in the presence or absence of 10 mg C/L of qualitatively different natural organic matter (NOM) derived from water spanning a large gradient in hydrologic residence time. Accumulation of Cu by trout gills was compared to Cu speciation determined by ion selective electrode (ISE) and by diffusive gradients in thin films (DGT) gel sampler technology. The presence of NOM decreased Cu uptake by trout gills as well as Cu concentrations determined by ISE and DGT. Furthermore, the source of NOM influenced Cu binding by trout gills with high-color, allochthonous NOM decreasing Cu accumulation by the gills more than low-color autochthonous NOM. The pattern of Cu binding to the NOM measured by Cu ISE and by Cu accumulation by DGT samplers was similar to the fish gill results. A simple Cu−gill binding model required an NOM Cu-binding factor ( F ) that depended on NOM quality to account for observed Cu accumulation by trout gills; values of F varied by a factor of 2. Thus, NOM metal-binding quality, as well as NOM quantity, are both important when assessing the bioavailability of metals such as Cu to aquatic organisms.

Environmental Science & Technology↗

Evaluation of current techniques for isolation of chars as natural adsorbents

Chars in soils or sediments may potentially influence the soil/sediment sorption behavior. Current techniques for the isolation of black carbon including chars rely often on acid demineralization, base extraction, and chemical oxidation to remove salts and minerals, humic acid, and refractory kerogen, respectively. Little is known about the potential effects of these chemical processes on the char surface and adsorptive properties. This study examined the effects of acid demineralization, base extraction, and acidic Cr2O72- oxidation on the surface areas, surface acidity, and benzene adsorption characteristics of laboratory-produced pinewood and wheat-residue chars, pure or mixed with soils, and a commercial activated carbon. Demineralization resulted in a small reduction in the char surface area, whereas base extraction showed no obvious effect. Neither demineralization nor base extraction caused an appreciable variation in benzene adsorption and presumably the char surface properties. By contrast, the Cr2O 72- oxidation caused a >31% reduction in char surface area. The Boehm titration, supplemented by FTIR spectra, indicated that the surface acidity of oxidized chars increased by a factor between 2.3 and 12 compared to nonoxidized chars. Benzene adsorption with the oxidized chars was lower than that with the non-oxidized chars by a factor of >8.9; both the decrease in char surface area and the increase in char surface acidity contributed to the reduction in char adsorptive power. Although the Cr 2O72- oxidation effectively removes resistant kerogen, it is not well suited for the isolation of chars as contaminant adsorbents because of its destructive nature. Alternative nondestructive techniques that preserve the char surface properties and effectively remove kerogen must be sought.

Environmental Science & Technology↗

Long-term natural attenuation of carbon and nitrogen within a groundwater plume after removal of the treated wastewater source

Disposal of treated wastewater for more than 60 years onto infiltration beds on Cape Cod, Massachusetts produced a groundwater contaminant plume greater than 6 km long in a surficial sand and gravel aquifer. In December 1995 the wastewater disposal ceased. A long-term, continuous study was conducted to characterize the post-cessation attenuation of the plume from the source to 0.6 km downgradient. Concentrations and total pools of mobile constituents, such as boron and nitrate, steadily decreased within 1-4 years along the transect. Dissolved organic carbon loads also decreased, but to a lesser extent, particularly downgradient of the infiltration beds. After 4 years, concentrations and pools of carbon and nitrogen in groundwater were relatively constant with time and distance, but substantially elevated above background. The contaminant plume core remained anoxic for the entire 10-year study period; temporal patterns of integrated oxygen deficit decreased slowly at all sites. In 2004, substantial amounts of total dissolved carbon (7 mol C m-2) and fixed (dissolved plus sorbed) inorganic nitrogen (0.5 mol N m-2) were still present in a 28-m vertical interval at the disposal site. Sorbed constituents have contributed substantially to the dissolved carbon and nitrogen pools and are responsible for the long-term persistence of the contaminant plume. Natural aquifer restoration at the discharge location will take at least several decades, even though groundwater flow rates and the potential for contaminant flushing are relatively high.

Environmental Science & Technology↗

Using chromate to investigate the impact of natural organics on the surface reactivity of nanoparticulate magnetite

Chromate was used as a chemical probe to investigate the size-dependent influence of organics on nanoparticle surface reactivity. Magnetite–chromate sorption experiments were conducted with ∼90 and ∼6 nm magnetite nanoparticles in the presence and absence of fulvic acid (FA), natural organic matter (NOM), and isolated landfill leachate (LL). Results indicated that low concentrations (1 mg/L) of organics had no noticeable impact on chromate sorption, whereas concentrations of 50 mg/L or more resulted in decreased amounts of chromate sorption. The adsorption of organics onto the magnetite surfaces interfered equally with the ability of the 6 and 90 nm particles to sorb chromate from solution, despite the greater surface area of the smaller particles. Results indicate the presence of organics did not impact the redox chemistry of the magnetite–chromate system over the duration of the experiments (8 h), nor did the organics interact with the chromate in solution. Brunauer–Emmett–Teller (BET) and scanning electron microscopy (SEM) results indicate that the organics blocked the surface reactivity by occupying surface sites on the particles. The similarity of results with FA and NOM suggests that coverage of the reactive mineral surface is the main factor behind the inhibition of surface reactivity in the presence of organics.

Environmental Science & Technology↗

Geochemistry of inorganic nitrogen in waters released from coal-bed natural gas production wells in the Powder River Basin, Wyoming

Water originating from coal-bed natural gas (CBNG) production wells typically contains ammonium and is often disposed via discharge to ephemeral channels. A study conducted in the Powder River Basin, Wyoming, documented downstream changes in CBNG water composition, emphasizing nitrogen-cycling processes and the fate of ammonium. Dissolved ammonium concentrations from 19 CBNG discharge points ranged from 95 to 527 μM. Within specific channels, ammonium concentrations decreased with transport distance, with subsequent increases in nitrite and nitrate concentrations. Removal efficiency, or uptake, of total dissolved inorganic nitrogen (DIN) varied between channel types. DIN uptake was greater in the gentle-sloped, vegetated channel as compared to the incised, steep, and sparsely vegetated channel and was highly correlated with diel patterns of incident light and dissolved oxygen concentration. In a larger main channel with multiple discharge inputs ( n = 13), DIN concentrations were >300 μM, with pH > 8.5, after 5 km of transport. Ammonium represented 25−30% of the large-channel DIN, and ammonium concentrations remained relatively constant with time, with only a weak diel pattern evident. In July 2003, the average daily large-channel DIN load was 23 kg N day −1 entering the Powder River, an amount which substantially increased the total Powder River DIN load after the channel confluence. These results suggest that CBNG discharge may be an important source of DIN to western watersheds, at least at certain times of the year, and that net oxidation and/or removal is dependent upon the extent of contact with sediment and biomass, type of drainage channel, and time of day.

Wyoming↗

Problems associated with using filtration to define dissolved trace element concentrations in natural water samples

Field and laboratory experiments indicate that a number of factors associated with filtration other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample) can produce significant variations in the “dissolved” concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. The bulk of these variations result from the inclusion/exclusion of colloidally associated trace elements in the filtrate, although dilution and sorption/desorption from filters also may be factors. Thus, dissolved trace element concentrations quantitated by analyzing filtrates generated by processing whole water through similar pore-sized filters may not be equal or comparable. As such, simple filtration of unspecified volumes of natural water through unspecified 0.45-μm membrane filters may no longer represent an acceptable operational definition for a number of dissolved chemical constituents.

Environmental Science & Technology↗

Quantification of natural vapor fluxes of trichloroethene in the unsaturated zone at Picatinny Arsenal, New Jersey

The upward flux of trichloroethene (TCE) vapor through the unsaturated zone above a contaminated, water-table aquifer at Picatinny Arsenal, New Jersey, has been studied under natural conditions over a 12-month period. Vertical gas-phase diffusion fluxes were estimated indirectly by measuring the TCE vapor concentration gradient in the unsaturated zone and using Fick's law to calculate the flux. The total gas-phase flux (e.g., the sum of diffusion and advection fluxes) was measured directly with a vertical flux chamber (VFC). In many cases, the upward TCE vapor flux was several orders of magnitude greater than the upward TCE diffusion flux, suggesting that mechanisms other than steady-state vapor diffusion are contributing to the vertical transport of TCE vapors through the unsaturated zone. The measured total flux of TCE vapor from the subsurface to the atmosphere is approximately 50 kg/yr and is comparable in magnitude to the removal rate of TCE from the aquifer by an existing pump-and-treat system and by discharge into a nearby stream. The net upward flux of TCE is reduced significantly during a storm event, presumably due to the mass transfer of TCE from the soil gas to the infiltrating rainwater and its subsequent downward advection. Several potential problems associated with the measurement of total gas-phase fluxes are discussed.

Environmental Science & Technology↗

Comparison of denitrification activity measurements in groundwater using cores and natural-gradient tracer tests

The transport of many solutes in groundwater is dependent upon the relative rates of physical flow and microbial metabolism. Quantifying rates of microbial processes under subsurface conditions is difficult and is most commonly approximated using laboratory studies with aquifer materials. In this study, we measured in situ rates of denitrification in a nitrate-contaminated aquifer using small-scale, natural-gradient tracer tests and compared the results with rates obtained from laboratory incubations with aquifer core material. Activity was measured using the acetylene block technique. For the tracer tests, co-injection of acetylene and bromide into the aquifer produced a 30 μM increase in nitrous oxide after 10 m of transport (23−30 days). An advection−dispersion transport model was modified to include an acetylene-dependent nitrous oxide production term and used to simulate the tracer breakthrough curves. The model required a 4-day lag period and a relatively low sensitivity to acetylene to match the narrow nitrous oxide breakthrough curves. Estimates of in situ denitrification rates were 0.60 and 1.51 nmol of N 2 O produced cm - 3 aquifer day - 1 for two successive tests. Aquifer core material collected from the tracer test site and incubated as mixed slurries in flasks and as intact cores yielded rates that were 1.2−26 times higher than the tracer test rate estimates. Results with the coring-dependent techniques were variable and subject to the small-scale heterogeneity within the aquifer, while the tracer tests integrated the heterogeneity along a flow path, giving a rate estimate that is more applicable to transport at the scale of the aquifer.

Environmental Science & Technology↗

The interaction of natural organic matter with iron in a wetland (Tennessee Park, Colorado) receiving acid mine drainage

Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

Aquatic Geochemistry↗

Release from parasites as natural enemies: increased performance of a globally introduced marine crab

Introduced species often seem to perform better than conspecifics in their native range. This is apparent in the high densities they may achieve or the larger individual sizes they attain. A prominent hypothesis explaining the success of introduced terrestrial species is that they are typically free of or are less affected by the natural enemies (competitors, predators, and parasites) they encounter in their introduced range compared to their native range. To test this hypothesis in a marine system, we conducted a global assessment of the effect of parasitism and predation on the ecological performance of European green crab populations. In Europe, where the green crab is native, crab body size and biomass were negatively associated with the prevalence of parasitic castrators. When we compared native crab populations with those from introduced regions, limb loss (an estimator of predation) was not significantly lower in introduced regions, parasites infected introduced populations substantially less and crabs in introduced regions were larger and exhibited a greater biomass. Our results are consistent with the general prediction that introduced species suffer less from parasites compared to populations where they are native. This may partly explain why the green crab is such a successful invader and, subsequently, why it is a pest in so many places.

Biological Invasions↗