Fluctuations of dissolved organic matter in river used for drinking water and impacts on conventional treatment plant performance

Natural organic matter (NOM) in drinking water supplies can provide precursors for disinfectant byproducts, molecules that impact taste and odors, compounds that influence the efficacy of treatment, and other compounds that are a source of energy and carbon for the regrowth of microorganisms during distribution. NOM, measured as dissolved organic carbon (DOC), was monitored daily in the White River and the Indiana-American water treatment plant over 22 months. Other parameters were either measured daily (UV-absorbance, alkalinity, color, temperature) or continuously (turbidity, pH, and discharge) and used with stepwise linear regressions to predict DOC concentrations. The predictive models were validated with monthly samples of the river water and treatment plant effluent taken over a 2-year period after the daily monitoring had ended. Biodegradable DOC (BDOC) concentrations were measured in the river water and plant effluent twice monthly for 18 months. The BDOC measurements, along with measurements of humic and carbohydrate constituents within the DOC and BDOC pools, revealed that carbohydrates were the organic fraction with the highest percent removal during treatment, followed by BDOC, humic substances, and refractory DOC.     

Composite geochemical database for coalbed methane produced water quality in the Rocky Mountain region

Coalbed methane (CBM) or coalbed natural gas (CBNG) is an unconventional natural gas resource with large reserves in the United States (US) and worldwide. Production is limited by challenges in the management of large volumes of produced water. Due to salinity of CBM produced water, it is commonly reinjected into the subsurface for disposal. Utilization of this nontraditional water source is hindered by limited knowledge of water quality. A composite geochemical database was created with 3255 CBM wellhead entries, covering four basins in the Rocky Mountain region, and resulting in information on 64 parameters and constituents. Database water composition is dominated by sodium bicarbonate and sodium chloride type waters with total dissolved solids concentrations of 150 to 39,260 mg/L. Constituents commonly exceeding standards for drinking, livestock, and irrigation water applications were total dissolved solids (TDS), sodium adsorption ratio (SAR), temperature, iron, and fluoride. Chemical trends in the basins are linked to the type of coal deposits, the rank of the coal deposits, and the proximity of the well to fresh water recharge. These water composition trends based on basin geology, hydrogeology, and methane generation pathway are relevant to predicting water quality compositions for beneficial use applications in CBM-producing basins worldwide.     

Spatial variation of streamwater chemistry in two Swedish boreal catchments: implications for environmental assessment

To evaluate the scale-dependent spatial variability of water chemistry within two Swedish boreal catchments (subcatchment areas 0.01-78 km2), samples were taken at every junction in the stream network during June 2000 and August 2002. The values of most chemical constituents spanned more than an order of magnitude, and the range was similar to that found in all of Northern Sweden by the national stream survey in 2000. According to the official assessment tools used in Sweden, the entire range of environmental status (for pH, absorbance, alkalinity, dissolved organic carbon (DOC)) and human acidification influence existed within these two study catchments. The water chemistry parameters were relatively stable at catchment areas greater than 15 km2. Sampling at that scale may be adequate if generalized values for the landscape are desired. However the chemistry of headwaters, where much of the stream length and aquatic ecosystem is found would not be characterized. Map parameters correlated to the variability in a key chemical parameter, DOC, but the best predictive map parameters differed markedly between catchments. This study highlights the importance of accounting for headwater spatial variability in environmental assessments of running waters, even in relatively pristine areas. The nature of drainage networks with many headwaters and progressively fewer downstream watercourses makes this a considerable challenge.     

Change of dissolved gaseous mercury concentrations in a southern reservoir lake (Tennessee) following seasonal variation of solar radiation

A 12-month field study was conducted consecutively from June 2003 to May 2004 to quantify temporal variations of dissolved gaseous mercury (DGM) concentrations in Cane Creek Lake, a southern reservoir lake (Cookeville, TN). Diurnal changes of DGM concentrations in two periods (morning increase vs afternoon decrease with an around-noon peak) were observed, and the changes closely followed daily solar radiation variation trends. The diurnal patterns prevailed in the late spring and summer, but became vague in the late fall and winter. The monthly mean DGM concentrations peaked at 40.8 pg L(-1) in July and reached the lowest at 14.2 pg L(-1) in December and 21.9 pg L(-1) in January; this DGM concentration change closely followed the monthly mean solar radiation variation trend. The increase of the lake DGM concentration from January to July and its decrease from July to December mirror the typical daily rhythm of DGM concentration variations in the two periods. This finding supports the following hypothesis: The natural phenomenon of daily oscillation of freshwater DGM concentrations that follows diurnal solar radiation variation would manifest on a seasonal scale. High DGM concentrations were found in the spring and summer and low in the fall and winter (seasonal mean: 34.2, 37.5, 20.0, 24.4 pg L(-1), respectively). This seems to suggest an annual occurrence of two periods of the seasonal DGM level fluctuation (spring and summer high vs fall and winter low DGM levels). Linear relationships of the monthly mean DGM concentrations were found with the monthly mean global solar radiation (R2 = 0.82, P < 0.05) and UVA radiation (R2 = 0.84, P < 0.05). Linear relationships of the seasonal mean DGM concentrations were also found with the seasonal mean global solar radiation (R2 = 0.85, P = 0.08) and UVA radiation (R2 = 0.93, P < 0.05).     

Temporal variations and controlling factors of nitrogen export from an artificially drained coastal forest

Nitrogen losses in drainage water from coastal forest plantations can constrain the long term sustainability of the system and could negatively affect adjacent nutrient sensitive coastal waters. Based on long-term (21 years) field measurements of hydrology and water quality, we investigated the temporal variations and controlling factors of nitrate and dissolved organic nitrogen (DON) export from an artificially drained coastal forest over various time scales (interannual, seasonal, and storm events). According to results of stepwise multiple linear regression analyses, the observed large interannual variations of nitrate flux and concentration from the drained forest were significantly (p < 0.004) controlled by annual mean water table depth, and annual drainage or precipitation. Annual precipitation and drainage were found to be dominant factors controlling variations of annual DON fluxes. Temporal trends of annual mean DON concentration could not be explained explicitly by climate or hydrologic factors. No significant difference was observed between nitrogen (both nitrate and DON) export during growing and nongrowing seasons. Nitrate exhibited distinguished export patterns during six selected storm events. Peak nitrate concentrations during storm events were significantly (p < 0.003) related to 30-day antecedent precipitation index and the minimum water table depth during individual events. The temporal variations of DON export within storm events did not follow a clear trend and its peak concentration during the storm events was found to be significantly (p < 0.006) controlled by the short-term drying and rewetting cycles.     

Model assessment of biogeochemical controls on dissolved organic carbon partitioning in an acid organic soil

A chemical model (constructed in the ORCHESTRA modeling framework) of an organic soil horizon was used to describe soil solution data (10 cm depth) and assess if seasonal variations in soil solution dissolved organic carbon (DOC) could be explained by purely abiotic (geochemical controls) mechanisms or whether factors related to biological activity are needed. The NICA-Donnan equation is used to describe the competitive binding of protons and cations and the charge on soil organic matter. Controls on organic matter solubility are surface charge and a parameter, gamma, that accounts for the distribution of humic molecules between hydrophobic and hydrophilic fractions. Calculations show that the variations in solute chemistry alone are not sufficient to account for the observed variations of DOC, but factors that alter gamma, such as biological activity, are. Assuming that DOC in organic soils is derived from soluble humic material and that gamma is modified seasonally due to biological activity (with monthly soil temperature used as a surrogate for biological activity) we are able to model the observed seasonality of soil solution DOC over a 10-year period. Furthermore, with modeled DOC coupled to other geochemical processes we also model soil solution pH and Al concentrations.     

Chemical heterogeneity of organic soil colloids investigated by scanning transmission X-ray microscopy and C-1s NEXAFS microspectroscopy

Colloid release and deposition in soils and sorption of inorganic and organic pollutants to soil colloids are strongly influenced by the composition and chemical heterogeneity of colloidal soil particles. To investigate the chemical heterogeneity of organic soil colloids at the particle scale, we used synchrotron scanning transmission X-ray microscopy (STXM) and C-1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy on 49 individual particles isolated from the surface horizons of three forest soils. Stacks of 130 images of each particle were collected at different X-ray energies between 280 and 310 eV. From these image arrays, NEXAFS spectra were obtained for each pixel and analyzed by principle component analysis and cluster analysis (PCA-CA) to characterize the intraparticle heterogeneity of the organic components. The results demonstrate that the organic matter associated with water-dispersible soil colloids is chemically heterogeneous at the single-particle scale. PCA-CA identified at least two distinct regions within single particles. However, the spectral variations between these regions were much smaller than the variations of averaged NEXAFS spectra representing different particles from the same soil horizon, implying that interparticle heterogeneity is much larger than intraparticle heterogeneity. Especially the contents of aromatic and carboxyl carbon exhibited a large variability. Overall, the NEXAFS spectra of water-dispersible soil colloids were similar to the NEXAFS spectrum of the humic acid fraction, but differed clearly from the fulvic acid and dissolved organic matter fractions extracted from the same soil horizon using conventional techniques.     

Hypoxia in the Baltic Sea and basin-scale changes in phosphorus biogeochemistry

Deep-water oxygen concentrations in the Baltic Sea are influenced by eutrophication, but also by saltwater inflows from the North Sea. In the last two decades, only two major inflows have been recorded and the lack of major inflows is believed to have resulted in a long-term stagnation of the deepest bottom water. Analyzing data from 1970 to 2000 at the basin scale, we show that the estimated volume of water with oxygen, <2 mL L(-1), was actually at a minimum at the end of the longest so-called stagnation period on record. We also show that annual changes in dissolved inorganic phosphate water pools were positively correlated to the area of bottom covered by hypoxic water, but not to changes in total phosphorus load, thus addressing the legacy of eutrophication on a basinwide scale. The variations in phosphorus pools that have occurred during the past decades do not reflect any human action to reduce inputs. The long residence time and internally controlled variation of the large P pool in the Baltic Sea has important implications for management of both N and P inputs into this eutrophicated enclosed basin.     

Winter-time climatic control on dissolved organic carbon export and surface water chemistry in an Adirondack forested watershed

Although most of forested watersheds in temperate and boreal regions are snow-covered for a substantial portion of the year, responses of biogeochemical processes under the snow pack to climatic fluctuations are poorly understood. We investigated responses of dissolved organic carbon (DOC) and surface water chemistry in stream and lake discharge waters draining the Arbutus Lake Watershed in the Adirondacks of New York State to climatic fluctuations during the snow-covered months from December through April. Interannual variability in stream discharge corresponded to changes in air temperature and snow pack depth across the winter months. Concentrations of DOC in stream water draining a subcatchment showed immediate positive responses to rising temperatures and subsequent increases in runoff during most snowmelt events. Increases in DOC concentrations usually coincided with decreases in pH and increases in total aluminum (Al) concentrations, while the correlations between concentrations of DOC and SO4(2-) or base cations were negative. Although changes in air temperature, snow pack depth, and runoff were all significantly correlated with stream water concentrations of major solutes, stepwise linear regression found that runoff was the best predictor of solute concentrations. Results of stepwise linear regression with long-term monthly monitoring data collected at the lake outlet showed weaker but still consistent climatic effects on interannual variations in concentrations of DOC and other solutes. Over the 17 winter periods from December 1983 through April 2000, changes in seasonal average concentrations of DOC, H+, and Al in lake discharge generally corresponded to interannual variations in temperature, precipitation, and runoff, while SO4(2-) and base cations displayed an opposite trend. The results suggest that snowmelt-mediated DOC responses to temperature fluctuations during the winter months might offset increases in the surface water pH caused by decreasing acidic deposition and pose a potential hazard of Al toxicity in surface waters.     

Climatic, biological, and land cover controls on the exchange of gas-phase semivolatile chemical pollutants between forest canopies and the atmosphere

An ecophysiological model of a structured broadleaved forest canopy was coupled to a chemical fate model of the air-canopy exchange of gaseous semivolatile chemicals to dynamically assess the short-term (hours) and medium term (days to season) air-canopy exchange and the influence of biological, climatic, and land cover drivers on the dynamics of the air-canopy exchange and on the canopy storage for airborne semivolatile pollutants. The chemical fate model accounts for effects of short-term variations in air temperature, wind speed, stomatal opening, and leaf energy balance, all as a function of layer in the canopy. Simulations showed the potential occurrence of intense short/medium term re-emission of pollutants having log K(OA) up to 10.7 from the canopy as a result of environmental forcing. In addition, relatively small interannual variations in seasonally averaged air temperature, canopy biomass, and precipitation can produce relevant changes in the canopy storage capacity for the chemicals. It was estimated that possible climate change related variability in environmental parameters (e.g., an increase of 2 °C in seasonally averaged air temperature in combination with a 10% reduction in canopy biomass due to, e.g., disturbance or acclimatization) may cause a reduction in canopy storage capacity of up to 15-25%, favoring re-emission and potential for long-range atmospheric transport. On the other hand, an increase of 300% in yearly precipitation can increase canopy sequestration by 2-7% for the less hydrophobic compounds.     

An estimate of the mean daily intake of glucosinolates from cruciferous vegetables in the UK

Samples (174) of cabbage, Brussels sprouts, cauliflower and swede-turnip have been analysed for total and individual glucosinolate content in both the fresh and cooked form. Using data from the 1980 National Food Survey, the national mean daily intake is calculated to be 46.1 mg in fresh material, and 29.4 mg in cooked. There are large variations within the UK (for example in Scotland it is less than half that in south-west of England), between income groups and over the year. National mean daily intake figures for the glucosinolates yielding goitrogenic products such as oxazolidine-2-thiones and thiocyanate ion are 6.7 and 14.7 mg respectively; the former figure is approximately doubled in the winter months. Based upon the above variations, arising from eating habits in the UK, together with the known large variation in glucosinolate content in cruciferous plants because of agronomic and environmental effects, it is likely that certain individuals will consume more than 300 mg total glucosinolates per day. The nutritional and toxicological consequences of such an intake are unknown at present.     

Comparative evaluation of the fate of disinfection byproducts at eight aquifer storage and recovery sites

Despite the growth in aquifer storage and recovery (ASR) as a technique for the provision of potable water supplies, quantitative data on the fate of disinfection byproducts that may be present in the injected water remain rare. This study evaluates the data from eight ASR sites in Australia and the United States that cover a wide range of source water compositions, hydrogeological environments, and operating conditions. Rates of attenuation and formation of trihalomethanes (THMs) in groundwater were determined using analytical techniques that took dilution effects into account. Half-lives varied by more than 2 orders of magnitude (e.g., <1 to >120 days for total THMs) and were both compound- and site- specific. Chloroform was most persistent, and more highly brominated compounds tended to be less persistent, as has generally been found. For any particular THM compound, much of the variability could be explained by contrasts in geochemical conditions within the aquifer since microbial degradation is the primary mechanism for THM attenuation. As such, bounds on the half-life were defined according to the redox state of the groundwater. In situ formation of some THMs in the aquifer after injection was directly observed at a number of sites, and was predicted to have taken place at all sites. The variance in formation estimates was large between the different methods used. Formation may be more common than previously thought because of the low frequency of groundwater sampling after injection and concomitant attenuation and mixing.     

Biogeochemical controls on Diel cycling of stable isotopes of dissolved O2 and dissolved inorganic carbon in the Big Hole River, Montana

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in 6180 of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13%o) cycles in delta18O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in delta18O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O2 and C budgets in rivers and may also be applicable to lake and groundwater systems.     

Designing hypolimnetic aeration and oxygenation systems--a review

When properly designed, hypolimnetic aeration and oxygenation systems can replenish dissolved oxygen in water bodies while preserving stratification. The three primary devices are the airlift aerator, Speece Cone, and bubble-plume diffuser. In each device, gas bubbles in contact with water facilitate interfacial transfer of oxygen, nitrogen, and other soluble gases. However, early design procedures for airlift aerators were empirical, while most bubble-plume models did not account for stratification or gas transfer. Using fundamental principles, a discrete-bubble model was first developed to predict plume dynamics and gas transfer for a circular bubble-plume diffuser. The discrete-bubble approach has subsequently been validated using oxygen transfer tests in a large vertical tank and applied successfully at full-scale to an airlift aerator as well as to both circular and linear bubble-plume diffusers. The performance of each of the four completely different full-scale systems (on a scale of 10 m or more) was predicted based on the behavior of individual bubbles (on a scale of about 1 mm). The combined results suggest thatthe models can be used with some confidence to predict system performance based on applied air or oxygen flow rate, initial bubble size, and, in the case of bubble plume diffusers, near-field boundary conditions. The discrete-bubble approach has also been extended to the Speece Cone, but the model has not yet been validated due to a lack of suitable data. The unified suite of models, all based on simple discrete-bubble dynamics, represents the current state-of-the-art for designing systems to add oxygen to stratified lakes and reservoirs.     

Precipitation and Temperature Effects on Mortality and Lactation Parameters of Dairy Cattle in California

Data from 3 commercial rendering companies located in different regions of California were analyzed from September 2003 through August 2005 to examine the relationship of dairy calf and cow mortality to monthly average daily temperature and total monthly precipitation respectively. Yearly average mortality varied between rendering regions from 2.1 to 8.1% for mature cows. The relationship between cow and calf monthly mortality and monthly average daily temperature was U-shaped. Overall, months with average daily temperatures less than 14 and greater than 24°C showed substantial increases in both calf and cow mortality with calf mortality being more sensitive to changes in these temperature ranges than cow mortality. Temperature changes were reflected in a 2-fold difference between the minimum and maximum mortality in cows and calves. Precipitation showed a weak effect with calf mortality and no effect with cow mortality. Data from Dairy Herd Improvement Association were used from 112 California herds tested over a 24-mo period to examine the relationship of milk production and quality with monthly average daily temperature and monthly precipitation. Somatic cell count and percent milk fat were either weakly or not associated with monthly average daily temperature and total monthly precipitation. However, total monthly precipitation was negatively associated with test day milk per milking cow regardless of the dairy's geographical location. Housing-specific associations for test day milk per milking cow were greater for total monthly precipitation than monthly average daily temperature, with the strongest negative association seen for dairies that do not provide shelter for cows. This suggests that providing suitable housing for lactating dairy cattle may ameliorate the precipitation-associated decrease in test day milk per milking cow.     

SEASONAL VARIABILITY OF CHEDDAR CHEESE WHEY POWDER: A CASE STUDY

Cheddar whey powder from one plant was evaluated for variations in quality parameters over 12 months. Representative samples were analyzed monthly for microbiological, physicochemical and sensory properties. The seasonal variability in the physicochemical properties was minor. Fall samples were higher in Hunter Lab parameter L* (lightness) and pH but lower in solubility index. Summer samples were high in solubility index and titratable acidity but low in L*. May production was significantly higher in standard plate count (SPC) and free moisture than the rest of the year. February production was significantly lower in SPC and free moisture content. There were no significant differences in aroma and flavor across the seasons. The flavor was generally bland, with the most intense attribute rating 5 on the 15‐point intensity scale. The order of intensity of the most intense attributes was cooked flavor and aroma > sweetness > caramelized flavor and aroma.     

Spatially complex distribution of dissolved manganese in a fjord as revealed by high-resolution in situ sensing using the autonomous underwater vehicle Autosub

Loch Etive is a fjordic system on the west coast of Scotland. The deep waters of the upper basin are periodically isolated, and during these periods oxygen is lost through benthic respiration and concentrations of dissolved manganese increase. In April 2000 the autonomous underwater vehicle (AUV) Autosub was fitted with an in situ dissolved manganese analyzer and was used to study the spatial variability of this element together with oxygen, salinity, and temperature throughout the basin. Six along-loch transects were completed at either constant height above the seafloor or at constant depth below the surface. The ca. 4000 in situ 10-s-average dissolved Mn (Mnd) data points obtained provide a new quasi-synoptic and highly detailed view of the distribution of manganese in this fjordic environment not possible using conventional (water bottle) sampling. There is substantial variability in concentrations (<25 to >600 nM) and distributions of Mnd. Surface waters are characteristically low in Mnd reflecting mixing of riverine and marine end-member waters, both of which are low in Mnd. The deeper waters are enriched in Mnd, and as the water column always contains some oxygen, this must reflect primarily benthic inputs of reduced dissolved Mn. However, this enrichment of Mnd is spatially very variable, presumably as a result of variability in release of Mn coupled with mixing of water in the loch and removal processes. This work demonstrates how AUVs coupled with chemical sensors can reveal substantial small-scale variability of distributions of chemical species in coastal environments that would not be resolved by conventional sampling approaches. Such information is essential if we are to improve our understanding of the nature and significance of the underlying processes leading to this variability.     

Landfill-stimulated iron reduction and arsenic release at the Coakley Superfund Site (NH)

Arsenic is a contaminant at more than one-third of all Superfund Sites in the United States. Frequently this contamination appearsto resultfrom geochemical processes rather than the presence of a well-defined arsenic source. Here we examine the geochemical processes that regulate arsenic levels at the Coakley Landfill Superfund Site (NH), a site contaminated with As, Cr, Pb, Ni, Zn, and aromatic hydrocarbons. Long-term field observations indicate that the concentrations of most of these contaminants have diminished as a result of treatment by monitored natural attenuation begun in 1998; however, dissolved arsenic levels increased modestly over the same interval. We attribute this increase to the reductive release of arsenic associated with poorly crystalline iron hydroxides within a glaciomarine clay layer within the overburden underlying the former landfill. Anaerobic batch incubations that stimulated iron reduction in the glaciomarine clay released appreciable dissolved arsenic and iron. Field observations also suggest that iron reduction associated with biodegradation of organic waste are partly responsible for arsenic release; over the five-year study period since a cap was emplaced to prevent water flow through the site, decreases in groundwater dissolved benzene concentrations at the landfill are correlated with increases in dissolved arsenic concentrations, consistent with the microbial decomposition of both benzene and other organics, and reduction of arsenic-bearing iron oxides. Treatment of contaminated groundwater increasingly is based on stimulating natural biogeochemical processes to degrade the contaminants. These results indicate that reducing environments created within organic contaminant plumes may release arsenic. In fact, the strong correlation (>80%) between elevated arsenic levels and organic contamination in groundwater systems at Superfund Sites across the United States suggests that arsenic contamination caused by natural degradation of organic contaminants may be widespread.     

Life cycle impact assessment of terrestrial acidification: modeling spatially explicit soil sensitivity at the global scale

This paper presents a novel life cycle impact assessment (LCIA) approach to derive spatially explicit soil sensitivity indicators for terrestrial acidification. This global approach is compatible with a subsequent damage assessment, making it possible to consistently link the developed midpoint indicators with a later endpoint assessment along the cause-effect chain-a prerequisite in LCIA. Four different soil chemical indicators were preselected to evaluate sensitivity factors (SFs) for regional receiving environments at the global scale, namely the base cations to aluminum ratio, aluminum to calcium ratio, pH, and aluminum concentration. These chemical indicators were assessed using the PROFILE geochemical steady-state soil model and a global data set of regional soil parameters developed specifically for this study. Results showed that the most sensitive regions (i.e., where SF is maximized) are in Canada, northern Europe, the Amazon, central Africa, and East and Southeast Asia. However, the approach is not bereft of uncertainty. Indeed, a Monte Carlo analysis showed that input parameter variability may induce SF variations of up to over 6 orders of magnitude for certain chemical indicators. These findings improve current practices and enable the development of regional characterization models to assess regional life cycle inventories in a global economy.     

Precipitates on granular iron in solutions containing calcium carbonate with trichloroethene and hexavalent chromium

Mineralogical examination, using scanning electron microscopy (SEM), X-ray diffractometry (XRD), and optical microscopy, was conducted on the Fe0-bearing reactive materials derived from long-term column experiments undertaken to assess the treatment capacity of Fe0 under different geochemical conditions. The columns received either deionized water or solutions of differing dissolved calcium carbonate concentrations, together either with trichloroethene (TCE) or hexavalent chromium (Cr(VI)). The major reaction product in the columns receiving deionized water was magnetite-maghemite, and for the columns receiving dissolved calcium carbonate, the main products were iron hydroxy carbonate and aragonite. Replacement of Fe0 by reaction products occurred mainly at the edges of the Fe0 particles, and penetrative replacement was focused along cracks and along and around graphitic inclusions. Fibrous or flake-shaped iron hydroxy carbonate mostly replaced the edges of the Fe0 particles. Aragonite had needle-shaped morphology, and some occurred as clusters of crystals. Aragonite was deposited on iron hydroxy carbonate, thus providing at least a partial armoring effect. The mineral was also observed to cement groups of Fe0 particles into compact aggregates. The Cr was present mostly as Cr(III) in Cr(III)-Fe(III) (oxy)hydroxides and in trace amounts in iron hydroxy carbonate.