Background Organic Matter Research Articles

Selective Oxidative Degradation of Organic Pollutants by Singlet Oxygen-Mediated Photosensitization: Tin Porphyrin versus C60 Aminofullerene Systems

This study evaluates the potential application of tin porphyrin- and C(60) aminofullerene-derivatized silica (SnP/silica and aminoC(60)/silica) as (1)O(2) generating systems for photochemical degradation of organic pollutants. Photosensitized (1)O(2) production with SnP/silica, which was faster than with aminoC(60)/silica, effectively oxidized a variety of pharmaceuticals. Significant degradation of pharmaceuticals in the presence of the 400-nm UV cutoff filter corroborated visible light activation of both photosensitizers. Whereas the efficacy of aminoC(60)/silica for (1)O(2) production drastically decreased under irradiation with λ > 550 nm, Q-band absorption caused negligible loss of the photosensitizing activity of SnP/silica in the long wavelength region. Faster destruction of phenolates by SnP/silica and aminoC(60)/silica under alkaline pH conditions further implicated (1)O(2) involvement in the oxidative degradation. Direct charge transfer mediated by SnP, which was inferred from nanosecond laser flash photolysis, induced significant degradation of neutral phenols under high power light irradiation. Self-sensitized destruction caused gradual activity loss of SnP/silica in reuse tests unlike aminoC(60)/silica. The kinetic comparison of SnP/silica and TiO(2) photocatalyst in real wastewater effluents showed that photosensitized singlet oxygenation of pharmaceuticals was still efficiently achieved in the presence of background organic matters, while significant interference was observed for photocatalyzed oxidation involving non-selective OH radical.

Recognizing and compensating for interference from the sediment’s background organic matter and biodegradation during interpretation of biomarker data from seafloor hydrocarbon seeps: An example from the Marco Polo area seeps, Gulf of Mexico, USA

A suite of seep samples from the vicinity of the Marco Polo field in the Green Canyon area of the Gulf of Mexico provides an exceptional opportunity to study the impact of interference from sediment background organic matter and alteration by biodegradation on thermogenic hydrocarbons from seafloor seeps. These seep samples contain a range in both the concentration of seeped hydrocarbons present and level of biodegradation experienced. In addition, the subsurface oil that sources the seepage was available for comparison. The results of the study show that it is essential to have the biomarker data from the sediment’s background organic matter when dealing with low concentration seepage. These data provide a means to characterize the contribution of background organic matter to the biomarker distributions. This, in turn, allows the identification of thermogenic hydrocarbons when the concentration of seeped oil in seafloor sediments is low. In high concentration seepage, the hopanes and regular steranes were found to be more susceptible to near-surface microbial alteration, while tricylic/tetracyclic terpanes, diasteranes, monoaromatic steroids, and triaromatic steroids were more resistant. If biodegradation is severe enough, all biomarker compounds are vulnerable to alteration and very little information is preserved. In an effort to reconstruct the altered distributions, low temperature pyrolysis of the seeped oils’ asphaltenes was done to liberate occluded biomarkers compounds. Although biomarkers were recovered, they did not resemble the parent oil. Characteristics of some of the recovered biomarker distributions suggest alteration by biodegradation. This implies the three dimensional structure of the asphaltenes may not offer complete protection from microbial attack. These results demonstrate why interpretation of biomarker data from seafloor seeps can be a difficult task. Care must be taken to recognize contributions from the sediment’s background organic matter as well as identify alteration by biodegradation. Failure to understand these processes can lead to erroneous interpretations being made about the seep’s parent oil and source rock.

Scale formation in reverse osmosis desalination: model development

Scale formation of soluble salts is one of the major factors limiting the performance of reverse osmosis (RO) membranes for desalination. In this study, a dynamic model based on the crystallization theory was developed to analyze the effect of CaSO 4 scale formation on RO desalination process. Taking into consideration two mechanisms in scale formation including surface and bulk crystallization, the performance of RO filtration was predicted as a function of crossflow velocity, transmembrane pressure, permeate recovery, and operation mode. The model results indicated that RO fouling due to surface crystallization is important in batch filtration whereas both surface and bulk crystallization is important in crossflow filtration. This is because concentration polarization is directly related to surface crystallization. RO fouling due to bulk crystallization appeared to increase with increasing crossflow velocity and permeate recovery. The effects of background organic matters and antiscalant on scale formation were quantified using the model. The effect of operating parameters on RO fouling and concentration polarization was explored based on the model analysis.

Effect of Pore-Blocking Background Compounds on the Kinetics of Trace Organic Contaminant Desorption from Activated Carbon

This study examined the effect of pore-blocking (PB) background organic matter, which is known to hinder adsorption kinetics, on the rate of trace contaminant desorption. Adsorption, displaced desorption (DD) and nondisplaced desorption (NDD) kinetic tests were performed using powdered activated carbon (PAC) that was preloaded with natural organic matter (NOM). Since the NOM contained both strongly competing (SC) and PB components, the proposed model separated the contributions of the SC and PB NOM to the overall diffusion coefficient of the target contaminant. By factoring outthe SC NOM contribution, which increases the overall diffusion coefficient it was found that the relationship used to model the effect of PB NOM on adsorption kinetics could also describe desorption kinetics. The results highlighted the substantial influence of competitive SC NOM on the kinetics of adsorption and desorption. SC NOM competition aids contaminant removal by offsetting the undesirable effects of pore blocking on adsorption kinetics. However, for desorption events, PB NOM serves a practical benefit of reducing the rate of release of adsorbed micropollutants, while SC NOM counters that gain by both displacing contaminants and accelerating their diffusion.

Improving fluorometry as a source tracking method to detect human fecal contamination

In a continuing effort to develop inexpensive source tracking methods to detect human fecal contamination in environmental waters, targeted sampling was combined with fluorometry. Targeted sampling works by identifying hot spots of fecal contamination through multiple samplings over ever-decreasing distances. Fluorometry identifies human fecal contamination by detecting optical brighteners, primarily from laundry detergents. Because organic matter fluoresces and interferes with fluorometry, two locations were chosen for sampling: waters relatively low in organic matter at Mayaguez Bay, Puerto Rico, and waters relatively high in organic matter at St. Simons Island, Georgia. In Puerto Rico, targeted sampling and fluorometry quickly and easily identified two hot spots of human fecal contamination in the Yaguez River, which flows through the city of Mayaguez. Another source tracking method, detection of theesp gene, confirmed their human origin. On St. Simous Island, targeted sampling and fiuorometry identified two hot spots of potential human fecal contamination. Detection of theesp gene confirmed the human origin of one site but not the other, most likely because background organic matter fluorescence interfered with fhiorometry. A separate experiment showed that adding a 436-um emission filter to the fluorometer reduced this background fluorescence by > 50%. With the 436-nm Filter in place, another sampling was conducted on St. Simons Island, and the second hot spot was identified as fecal contamination from birds. As long as the fluorometer was equipped with a 436-nm filter and organic matter concentrations were considered, targeted sampling combined with fluorometry was a relatively inexpensive method for identifying human fecal contamination in water.

Quantification and Modeling of the Elimination Behavior of Ecologically Problematic Wastewater Micropollutants by Adsorption on Powdered and Granulated Activated Carbon

The adsorption on powdered activated carbon (PAC) of ecotoxic or potentially ecotoxic micropollutants (ten pharmaceuticals, four X-ray contrast media, and eight industrial chemicals) present in a biologically treated municipal wastewater is studied. All but the X-ray contrast media are eliminated with high efficiency at an economically feasible PAC dosage of 10 mg/L. Based on the experimental data, the competition between the background organic matter and the micropollutant for the active sites of the adsorbent is modeled with the help of the adsorption and tracer analysis supported by the Ideal Adsorption Solution Theory. With granulated activated carbon, adsorption isotherms are determined by spiking. Based on these experimental data and modeled parameters, a lay-out of fixed-bed adsorbers may be simulated.

Reduction of Disinfection Byproduct Formation by Molecular Reconfiguration of the Fulvic Constituents of Natural Background Organic Matter

Experiments were performed to assess the effects of treating the fulvic acid fractions of background natural organic matter (NOM) by catalyst-induced oxidative coupling reactions. Changes in the molecular characteristics of the fulvic acids and related disinfection byproduct formation potentials of these important NOM constituents were investigated. The coupling reactions were induced by addition of horseradish peroxidase (HRP) and hydrogen peroxide to aqueous solutions of the fulvic acids (FAs) in semicontinuous flow reactors. Subsequent removal of organic matter by ultrafiltration was found to be markedly enhanced for FA solutions subjected to oxidative coupling treatment. Uniform formation condition tests further indicated that the disinfection byproducts formed upon chlorination of FAs treated via induced oxidative coupling were reduced significantly on a unit carbon basis relative to those formed upon chlorination of their untreated counterparts. Spectroscopic examinations revealed thatthe FA molecules were effectively reconfigured in the oxidative coupling reactions. Substantial conversion of aromatic hydroxyl groups into ether-bonded moieties is evident, and a loss of primary amine groups, probably through conversion into secondary or tertiary amines, was also observed. These conversions apparently result in cross-linking of the natural FA moieties to form stable species of larger sizes, thus rendering them more readily removable by ultrafiltration and less reactive with chlorine. The results of the study may be interpreted as indicating that catalytically induced oxidative coupling reactions of the type conducted in this work can be combined with ultrafiltration to provide an effective scheme for removal of disinfection byproduct precursors.

Simulating the performance of fixed-bed granular activated carbon adsorbers: Removal of synthetic organic chemicals in the presence of background organic matter

Granular activated carbon (GAC) adsorption is an effective treatment technology for the removal of synthetic organic chemicals (SOCs) from drinking water supplies. This treatment process can be expensive if not properly designed. Application of mathematical models is an attractive method to evaluate the impact of process variables on process design and performance. Practical guidelines were developed to select an appropriate model framework and to estimate site-specific model parameters to predict GAC adsorber performance. Pilot plant and field-scale data from 11 different studies were utilized to investigate the effectiveness of this approach in predicting adsorber performance in the presence of background organic batter (BOM). These data represent surface and ground water sources from four different countries. The modeling approach was able to adequately describe fixed-bed adsorber performance for the purpose of determining the carbon usage rate and process design variables. This approach is more accurate at predicting bed life in the presence of BOM than the current methods commonly used by practicing engineers.

Characterization procedure for adsorption of DOC (Dissolved Organic Carbon) from synthetic wastewater

A characterization method to evaluate the composition of background organic matters in terms of adsorbability was presented and applied to synthetic and domestic wastewater. The binomial distribution of DOC (Dissolved Organic Carbon) fraction in relation of a characterizing variable, the Freundlich coefficient, k, was proposed to describe the initial composition of wastewater by a finite number of pseudospecies. This method was tested for removal of DOC by using granular and powdered activated carbons. These experiments enable us to get information on the distribution function of species in the solution. From the results obtained in this work, kinetic experimental data were predicted on the assumption that the diffusion coefficients were unchanged during the experiments. It was confirmed to be effective in determining the initial composition and describing the equilibria of the DOC. From the experiments, it was found that this synthetic solution has a sigmoid type isotherm on activated carbons. This implies that there are two different adsorption regions in a system, favourable and unfavourable cases, depending on the solution concentration. This unfamiliar problem can be solved by using a characterization method based on IAST-Freundlich model.

Membrane filtration of two sulphonamides in tertiary effluents and subsequent adsorption on activated carbon

The adsorption behaviour of two polar organic micropollutants ( N- n-butylbenzenesulphonamide and sulphmethoxazole) onto powdered activated carbon (PAC) under competitive conditions prior to and after filtration with a tight ultrafiltration membrane was examined. The sulphonamides were spiked into microfiltered tertiary municipal effluent in μg L −1 quantities. Ultrafiltration of these effluents resulted in better adsorbability for both the micropollutants and the background organic matter in the permeates compared to the feed waters. This behaviour seems to be caused by a reduced blocking of micropores by lower concentrations of high molecular weight compounds in membrane filtrates. A combined treatment of ultrafiltration prior to adsorption can therefore reduce the carbon demand for potentially harmful micropollutants in effluents.

Effect of easily biodegradable organic compounds on bacterial growth in a bench-scale drinking water distribution system

Many engineered (e.g., disinfectant residual concentration) and environmental (e.g., temperature) factors influence bacterial regrowth in drinking water distribution systems. This paper examines the effect of nutrients, specifically biodegradable organic matter (BOM) composition, BOM concentration, and hydraulic retention time on bacterial growth in an annular reactor (AR). Drinking water that had an alkalinity of 300 mg/L as CaCO3and a free chlorine residual of approximately 0.2 mg/L was used as process water in the ARs. Prior to entering the ARs, the water was filtered through granular activated carbon (GAC) to remove background chlorine and background organic matter. A cocktail of easily biodegradable organic compounds consisting of carboxylic acids, aldehydes, and free amino acids were spiked into the ARs as the primary carbon source. It was found that the influent BOM concentration (p value = 0.013) and the presence of free amino acids in the BOM cocktail (p value = 0.009) significantly increased the number of viable culturable cells in the biofilm, as measured by heterotrophic plate counts (HPCs). The interaction between the BOM concentration and the presence of amino acids also significantly increased the number of biofilm HPCs (p value = 0.021). Alternatively, the BOM concentration and the amino acid fraction did not affect the number of bulk (i.e., suspended) bacteria. The number of biofilm HPCs in the reactor was approximately 10 times greater than the number of bulk HPCs at high influent BOM concentrations and low retention times (i.e., high BOM loading rates). At low loading rates, the ratio of number of biofilm to bulk cells was less than 2. Consequently, it was deduced that the BOM was utilized predominately by the biofilm cells. This indicates that removal of easily biodegradable organic compounds is an important factor for controlling biofilm growth in distribution systems.Key words: drinking water, distribution systems, biofilm, annular reactor, regrowth.

Atrazine removal by preloaded GAC

Utilities can use predictions of remaining GAC life to develop a GAC regeneration or replacement schedule.The effect of granular activated carbon (GAC) service time on the remaining life of GAC adsorbers that are exposed to periodic pollutant episodes was evaluated. Equilibrium and kinetic parameters describing the adsorption of atrazine were determined for GAC that had been preloaded with background organic matter (BOM) for as long as 25 months. Furthermore, atrazine removal was measured in pilot tests employing GAC that had been preloaded for five and 20 months. Isotherm data showed that (1) preloaded BOM sharply reduced the remaining adsorption capacity of GAC for atrazine, (2) competitive adsorption was not important on the tested preloaded GAC samples, and (3) use of pulverized preloaded GAC led to an overestimate of remaining adsorption capacity. Preloading had the greatest effect on GAC capacity; adsorption kinetics were not affected as severely. The homogeneous surface diffusion model was used to predict atrazine removal in pilot tests and to predict remaining GAC life. For the given adsorbent and background water, remaining life predictions for atrazine removal are presented for scenarios that may be typical for utilities in the midwestern United States and in western Europe.

Removal and Destruction of Organic Contaminants in Water Using Adsorption, Steam Regeneration, and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563. In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix. In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO2 photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed. In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.

Effect of preadsorbed background organic matter on granular activated carbon adsorption of atrazine

This study examines the effect of preadsorbed background organic matter (measured as dissolved organic carbon, DOC) on the granular activated carbon (GAC) adsorption of atrazine. Thirty-four experiments were conducted in batch contactors using organic-free laboratory water (<0.1 mg/l DOC) and pilot-column GAC, preloaded with DOC for 3–20 weeks (equivalent to 4.3–32 mg DOC/g GAC). Freundlich isotherms were determined for adsorption of atrazine at initial concentrations from 10 to 1000 μg/l. The isotherm data indicate that GAC capacities for atrazine are only moderately reduced by preadsorbed DOC. At an initial concentration of 1000 μg/l atrazine, the GAC capacity for atrazine decreases by −1.0 mg atz/mg preadsorbed DOC. At an initial concentration of 10 μg/l atrazine, the GAC capacity for atrazine decreases by only −0.40 mg atz/mg preadsorbed DOC. For the pilot-column GAC preloaded with a maximum of 32 mg DOC/g GAC, the decrease in capacity for atrazine averages −33±13%.

The effect of preloading on rapid small-scale column test predictions of atrazine removal by GAC adsorbers

Rapid small-scale column tests (RSSCTs) were evaluated for their ability to predict atrazine removal in pilot-scale granular activated carbon (GAC) adsorbers. The performance of both virgin and preloaded GACs was tested. Atrazine removal by virgin GAC was studied in post-filter adsorbers at Toulouse, France, and Choisy-le-Roi, France, using empty-bed contact times (EBCTs) of 10.3 and 14 min, respectively. For virgin GAC, RSSCTs successfully simulated atrazine removal over large-scale operating times of about 3.5–7 months. However, RSSCTs significantly overestimated atrazine removal at longer operating times. Atrazine removal by preloaded GAC was studied in pilot-scale post-filter adsorbers at Choisy-le-Roi, France, after preloading times of 5 months and 20 months. EBCTs were approximately 8.5 min. To describe the performance of pilot-scale adsorbers containing preloaded GAC, RSSCTs were initiated with virgin activated carbon, and preloading was simulated prior to the spiking of atrazine. For a pilot-scale adsorber containing GAC that had been preloaded for 5 months, the RSSCT data effectively described atrazine removal. However, the RSSCT was not successful in predicting atrazine removal by GAC after a preloading time of 20 months. Discrepancies between RSSCT and pilot data for long service times or after extended preloading periods may have been due to enhanced adsorption of background organic matter in the presence of oxygen. Overall, RSSCTs were judged to be most useful for predicting the initial performance of adsorbers containing virgin GAC.

Effect of ozonation on preloading of background organic matter in granular activated carbon filters

Background Organic Matter (BOM) preloading is adsorption of BOM onto Granular Activated Carbon (GAC) prior to the adsorption of target compounds, such as pesticides and other organic micropollutants (e.g. atrazine). BOM preloading is commonly found to speed up the breakthrough of target compounds during GAC filtration. Ozonation of GAC filter influent may be expected to lower BOM preloading, because it results in less adsorbable and more biodegradable BOM compounds. Short Fixed Bed (SFB) tests with virgin and preloaded GAC, performed within this study, confirmed that preloading of BOM present in pretreated river Rhine water speeds up the breakthrough of atrazine in GAC filters. BOM preloading was found to lower equilibrium adsorption capacity of GAC for atrazine, and to slow down both external and internal mass transfer rate of atrazine on/into GAC. Adsorption capacity of (crushed) GAC was determined from atrazine adsorption isotherms, while mass transfer rate coefficients were determined by fitting the Homogeneous Surface Diffusion model to the breakthrough of atrazine in the SFB tests. More pronounced BOM preloading was found in the GAC filter receiving non-ozonated influent than in its ozonated counterpart. Biodegradation of ozonated BOM was shown to lower BOM preloading in GAC filters.

Effect of ozonation on preloading of background organic matter in granular activated carbon filters

Background Organic Matter (BOM) preloading is adsorption of BOM onto Granular Activated Carbon (GAC) prior to the adsorption of target compounds, such as pesticides and other organic micropollutants (e.g. atrazine). BOM preloading is commonly found to speed up the breakthrough of target compounds during GAC filtration. Ozonation of GAC filter influent may be expected to lower BOM preloading, because it results in less adsorbable and more biodegradable BOM compounds. Short Fixed Bed (SFB) tests with virgin and preloaded GAC, performed within this study, confirmed that preloading of BOM present in pretreated river Rhine water speeds up the breakthrough of atrazine in GAC filters. BOM preloading was found to lower equilibrium adsorption capacity of GAC for atrazine, and to slow down both external and internal mass transfer rate of atrazine on/into GAC. Adsorption capacity of (crushed) GAC was determined from atrazine adsorption isotherms, while mass transfer rate coefficients were determined by fitting the Homogeneous Surface Diffusion model to the breakthrough of atrazine in the SFB tests. More pronounced BOM preloading was found in the GAC filter receiving non-ozonated influent than in its ozonated counterpart. Biodegradation of ozonated BOM was shown to lower BOM preloading in GAC filters.

Technical Note: Interference of Br−, BrO3−, and ClO3− with DOX determination

In the dissolved organic halogen (DOX) analytic test, prior to combustion, the granular activated carbon (GAC) on which the DOX is absorbed is washed with a sodium nitrate solution designed to remove any inorganic chloride that may have also adsorbed to the GAC. Thus, a potential positive interference is removed. This study investigated the effectiveness of the nitrate wash in eliminating possible interferences from bromide, bromate, and chlorate ions. No interference was detected from bromate or chlorate ion, but a small positive interference of about 12 micrograms Cl-/L per mg/L of bromide ion was found in the presence of background organic matter.

Effect of influent oxygen concentration on the GAC adsorption of VOCs in the presence of BOM

Two rapid small-scale column tests (RSSCTs) were conducted in combination with a large column adsorber to determine if the small columns could predict the performance of a large column. The adsorbate solution consisted of three volatile organic chemicals (VOCs) in the presence of background organic matter (BOM). Landfill leachate was used as the BOM source. Dissolved molecular oxygen was used as a parametric viriable in the column studies to determine its influence on the breakthrough behavior of the adsorbate solution. The RSSCT, designed according to the assumption of no dependency of the intraparticle surface diffusion coefficient on the activated carbon particle size, accurately predicted the performance of the large column under anoxic conditions (absence of molecular oxygen), but failed to predict its performance under ambient (8 mg 1 −1 dissolved oxygen) or oxic conditions (30 mg 1 −1 dissolved oxygen). The RSSCT, designed according to the assumption of a linear dependency of the intraparticle surface diffusion coefficient on the activated carbon particle size, accurately predicted the performance of the large column under oxic and ambient conditions, but failed to predict its performance under anoxic conditions. The presence of molecular oxygen in the test environment resulted in an increased adsorption of the BOM on the GAC surface, which in turn, decreased the capacity of the VOCs due to competitive effects.

Point-of-entry adsorbers for the removal of fumigants

Point-of-entry systems with granular activated carbon filters have been used extensively to provide safe water to rural homes with wells contaminated with synthetic organic chemicals. Because of the low cost of these systems, their design is generally based on the equilibrium column model, the isotherm data from the literature, and a scale-up factor. This paper analyzes the necessary scale-up factors for point-of-entry adsorbers based on fumigant adsorption data gathered through an extensive literature review. The fumigants evaluated are 1,2-dichloropropane, 1,2-dibromo-3-chloropropane, and ethylene dibromide. It was impossible to thoroughly assess the scale-up factors for 1,2-dichloropropane because of the limited data. Column data for the other two fumigants were sufficient to generate column loading lines, which can be used directly without resorting to scale-up factors. Column data showed that the scale-up factors are greatly affected by competitive adsorption with the naturally occurring background organic matter and by preloading of these organic matter. As these phenomena are not well understood, it is presently impossible to accurately predict the appropriate scale-up factors. A recommended design approach is outlined. Key words: adsorption, activated carbon, fumigants, point-of-entry.