Sorbed atrazine shifts into non-desorbable sites of soil organic matter during aging

Soil-chemical contact time (aging) is an important determinant of the sorption and desorption characteristics of the organic contaminants and pesticides in the environment. The effects of aging on mechanism-specific sorption and desorption of atrazine were studied in soil and clay slurries. Sorption isotherm and desorption kinetic experiments were performed, and soil-water distribution coefficients and desorption rate parameters were evaluated using linear and non-linear sorption equations and a three-site desorption model, respectively. Aging time for sorption of atrazine in sterilized soil and clay slurries ranged from 2 days to 8 months. Atrazine sorption isotherms were nearly linear (r(2)>0.97) and sorption coefficients were strongly correlated to soil organic carbon content. Sorption distribution coefficients (K(d)) increased with increase in age in all five soils studied, but not for K-montmorillonite. Sorption non-linearity did not increase with increase in age except for the Houghton muck soil. Desorption profiles were well described by the three-site desorption model. The equilibrium site fraction (f(eq)) decreased and the non-desorbable site fraction (f(nd)) increased as a function of aging time in all soils. For K-montmorillonite, f(nd) approximately 0 regardless of aging, showing that aging phenomena are sorbent/mechanism specific. In all soils, it was found that when normalized to soil organic matter content, the concentration of atrazine in desorbable sites was relatively constant, whereas that in non-desorbable site increased. This, and the lack of aging effects on desorption from montmorillonite, suggests that sorption into non-desorbable sites of soil organic matter is primary source of increased atrazine sorption in soils during aging.     

Partitioning of hydrophobic organic compounds within soil-water-surfactant systems

Understanding the partitioning of hydrophobic organic compounds (HOCs) within soil-water-surfactant systems is key to improving the use of surfactants for remediation. The overall objective of this study was to investigate the soil properties that influence the effectiveness of surfactants used to remediate soil contaminated with hydrophobic pesticides, as an example of a more general application for removing strongly sorbing HOCs from contaminated soils via in-situ enhanced sorption, or ex-situ soil washing. In this study, the partitioning of two commonly used pesticides, atrazine and diuron, within soil-water-surfactant systems was investigated. Five natural soils, one nonionic surfactant (Triton-100 (TX)) and one cationic surfactant (benzalkonium chloride (BC)) were used. The results showed that the cation exchange capacity (CEC) is the soil property that controls surfactant sorption onto the soils. Diuron showed much higher solubility enhancement than atrazine with the micelles of either surfactant. Within an ex-situ soil washing system, TX is more effective for soils with lower CEC than those with higher CEC. Within an in-situ enhanced sorption zone, BC works significantly better with more hydrophobic HOCs. The HOC sorption capacity of the sorbed surfactant (K(ss)) was a non-linear function of the amount of surfactant sorbed. For the cationic surfactant (BC), the maximal K(ss) occurred when around 40% of the total CEC sites in the various soils were occupied by sorbed surfactant. Below a sub-saturation sorption range (~20 g/kg), under the same amount of BC sorbed, a soil with lower CEC tends to have higher K(ss) than the one with higher CEC.     

Contact-time-dependent atrazine residue formation in surface soils

The formation of nonextractable atrazine residues was evaluated in sterilized agricultural and woodland soils pre-loaded with ¹⁴C-atrazine for contact periods of 1 h (0.046 days), and 1, 7, 14, 28, 56, and 84 days. Extractability of the pre-loaded atrazine and nonextractable residue formation were determined by subjecting the soils to sequential fill-and-draw extractions with water, ethylacetate/water, and alkali. Nonextractable atrazine residues associated with the fulvic acid (FA), humic acid (HA) and humin/mineral (HM) components of soil were determined by separating FA and HA from the soils and measuring the ¹⁴C-activity associated with each fraction. Longer herbicide–soil contact times resulted in attenuated water extractability and enhanced nonextractable residue formation. At the longest contact periods, residues recovered in the FA, HA and HM components of soil accounted for 35–50% of the pre-loaded herbicide. The woodland soil contained significantly larger amounts of HA and humin than the agricultural soil, and appeared to have contributed significantly to nonextractable residue formation. Results from this study indicate that physicochemical processes occurring at intra-mineral and intra-organic matter sites continue to influence the fate of organic pesticides long after their application on soils.     

Sorption and desorption of atrazine and diuron onto water dispersible soil primary size fractions

In this study, a low energy separation method was employed to separate water dispersible clay-, silt-, and sand-sized fractions. The batch equilibrium method was used to conduct atrazine and diuron sorption/desorption experiments with the bulk soils and their size fractions separately. A Freundlich sorption model provided the best fit for all sorption and desorption data. A mass balance calculation, taking into account the pesticide concentration differences in the size fraction and bulk soil, showed that pesticide sorption onto the different size fractions reproduces well the total amount of the pesticide sorbed onto the bulk soils. Due to their higher soil organic carbon content, the clay fractions were much more effective sorbents for the pesticides than the bulk soils, silt, and sand fractions. For all soils, the amount of the pesticide sorbed onto the clay fractions was more than 20% of the total amount of the pesticide sorbed by the bulk soils even though the clay fractions in these soils were only 5.3-14.0% (by weight). The clay fractions had the highest desorption hysteresis among all size fractions and the bulk soils, followed by silt fractions, implying the clay fractions had the strongest bound and least desorbable pesticide molecules. Our results suggest that attention should be paid to the pesticide sorbed to the smallest colloids, the water dispersible fraction, which can be potentially mobilized under field conditions, leading to wide spreading of contamination.     

Improved retention of imidacloprid (Confidor) in soils by adding vermicompost from spent grape marc

Batch sorption experiments of the insecticide imidacloprid by ten widely different Spanish soils were carried out. The sorption was studied for the active ingredient and its registered formulation Confidor. The temperature effect was studied at 15 degrees C and 25 degrees C. The addition of a vermicompost from spent grape marc (natural and ground), containing 344 g kg(-1) organic carbon, on the sorption of imidacloprid by two selected soils, a sandy loam and a silty clay loam, having organic carbon content of 3.6 g kg(-1) and 9.3 g kg(-1), respectively, was evaluated. Prior to the addition of this vermicompost, desorption isotherms with both selected soils, were also performed. The apparent hysteresis index (AHI) parameter was used to quantify sorption-desorption hysteresis. Sorption coefficients, K(d) and K(f), for the active ingredient and Confidor(R) in the different soils were similar. Sorption decreased with increasing temperature, this fact has special interest in greenhouse systems. A significant correlation (R(2)=0.965; P<0.01) between K(f) values and the organic carbon (OC) content was found, but some soils showed higher sorption coefficients than that expected from their OC values. The normalized sorption coefficients with the soil organic carbon content (K(oc)) were dispersed and low, implying that other characteristics of soils could contribute to the retention capacity as well. The spent grape marc vermicompost was an effective sorbent of this insecticide (K(f)=149). The sorption of imidacloprid increased significantly in soils amended with this vermicompost. The most pronounced effect was found in the sandy loam soil with low OC content, where the addition of 5% and 10% of vermicompost increased K(f) values by 8- and 15-fold, respectively. Soil desorption of imidacloprid was slower for the soil with the higher OC and clay content.     

Soil particle-size dependent partitioning behavior of pesticides within water-soil-cationic surfactant systems

Cationic surfactants have been proposed for enhanced sorption zones to contain hydrophobic organic compound (HOC) contamination. Benzalkonium chloride (BC), a cationic surfactant, was selected to study the particle-size dependent sorption behavior of the surfactant and its role in the immobilization of two hydrophobic pesticides (atrazine and diuron) within soil-water-surfactant systems for this application. Five different soils were considered in this study. Our results showed significant particle-size dependent behavior for surfactant sorption and pesticide immobilization in the presence of the sorbed cationic surfactant. The cation exchange capacity (CEC) of the bulk soils and their size fractions (clay, silt, and sand fractions) determined BC sorption capacity. In the absence of BC the sand fractions were the least effective sorbent for the pesticides compared with silts and clays. However, at relatively low BC mass sorbed (<10,000mg/kg) to any of the soil fractions, well below sorption saturation, the sand fractions became more effective sorbents for either pesticide than the clay and silt fractions. The pesticide partitioning coefficient onto sorbed BC (K(ss)) was not constant. Particle CEC, availability of CEC sites for sorption of the cationic surfactant, and the amount of the BC sorbed determined the phase of K(ss). The maximum K(ss) occurred before BC saturation sorption capacity was reached and at different % CEC occupancy for the different size fractions. For the clay fractions, the maximum K(ss) occurred at lower % CEC occupancy ( approximately 30-40%) than for the silt and sand fractions. The maximal K(ss) for the sand fractions occurred at the highest % CEC occupancy among all fractions ( approximately 50-60%). These findings suggest that for an in situ surfactant-enhanced sorption zone it may be better to operate well below the saturation sorption of the cationic surfactant. This would enhance sorption of the HOCs onto the immobile fractions (silt and sand fractions) rather than the potentially mobile clay fractions.     

Long-term sewage sludge application and wastewater irrigation on the mineralization and sorption of 17beta-estradiol and testosterone in soils

The disposal of animal manures, wastewater and sewage sludge to agricultural land can lead to the transfer of steroid hormones like 17beta-estradiol and testosterone into soils, surface and groundwaters. The objective of this study was to investigate the effects of different site histories like wastewater irrigation and sewage sludge application on hormone mineralization and sorption in soils. Two agricultural sites with different long-term treatment histories with wastewater and sewage sludge were sampled. The mineralization of (14)C-17beta-estradiol and (14)C-testosterone was studied during incubations at 20 degrees C over three weeks. Despite the structural resemblance of both hormones the mineralization rate of 17beta-estradiol was about an order of magnitude lower than that of testosterone in all four soils, reaching 5-7% vs. 50-59%, respectively. Estradiol mineralization was significantly lower in soils with long-term wastewater irrigation than in the corresponding soil with freshwater irrigation. Pre-incubation of the soils with unlabeled hormones or application of the hormones within a wastewater matrix had only minor effects on their mineralization. The results indicate that estradiol mineralization occurs co-metabolically and is limited by sorption, whereas testosterone appears to be utilized directly by soil microorganisms. Sorption of (14)C-17beta-estradiol and (14)C-testosterone to sterile and unsterile soils was determined in batch experiments with CaCl(2) or wastewater solution with hormone concentrations of 0.13-0.0013 mug mg(-1). FREUNDLICH sorption isotherms and parameters like K(F) and log K(oc) values were used to describe the results. The K(F) values for estradiol sorption were generally about 1.2 to 1.6-fold higher than for testosterone. The SOC-normalized partition coefficients K(oc) also differ accordingly and indicate quite large differences in soil organic matter qualities relating to hormone sorption between the soils and treatments. When the hormones were added to the soil within a wastewater matrix less estradiol was sorbed in the solid phase than in the controls with pure water, thus indicating that wastewater contains soluble sorbents.     

Untersuchungen zur Sorptionsreversibilität von organischen Schadstoffen in Aktivkohle, Holzkohle und Zeolith Y-200

Numerous studies have shown that sorption of organic contaminants in soils is dominated by the natural organic carbon content (C _org) of the soil. However, it is still under discussion whether sorption processes are fully reversible or whether an irreversibly sorbed contaminant fraction remains in the soil. This is especially important when considering soil remediation measures and its targets. In multi-stage sorption-desorption batch experiments with TCE, PCE, ortho-xylene and para-xylene and with the sorbents activated carbon, charcoal and a hydrophobic zeolite Y-200, the reversibility of sorption was studied. It could be shown that the structural features of the sorbents are of ample importance for the occurrence of a desorption-resistant fraction. While sorption was mainly reversible for the micro-porous zeolite Y-200 with a rigid pore network, charcoal and the activated carbon showed significant desorption hysteresis. However, following a subsequent sorption step, this fraction eventually desorbs and is re-mobilized.     

Effect of soil composition and dissolved organic matter on pesticide sorption

The effect of the solid and dissolved organic matter fractions, mineral composition and ionic strength of the soil solution on the sorption behaviour of pesticides were studied. A number of soils, chosen so as to have different clay mineral and organic carbon content, were used to study the sorption of the pesticides atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), 2,4-D ((2,4-dichlorophenoxy)acetic acid), isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) and paraquat (1,1'-dimethyl-4,4'-bipyridinium) in the presence of low and high levels of dissolved organic carbon and different background electrolytes. The sorption behaviour of atrazine, isoproturon and paraquat was dominated by the solid state soil components and the presence of dissolved organic matter had little effect. The sorption of 2,4-D was slightly affected by the soluble organic matter in the soil. However, this effect may be due to competition for adsorption sites between the pesticide and the soluble organic matter rather than due to a positive interaction between the pesticide and the soluble fraction of soil organic matter. It is concluded that the major factor governing the sorption of these pesticides is the solid state organic fraction with the clay mineral content also making a significant contribution. The dissolved organic carbon fraction of the total organic carbon in the soil and the ionic strength of the soil solution appear to have little or no effect on the sorption/transport characteristics of these pesticides over the range of concentrations studied.     

Partitioning of hydrophobic pesticides within a soil-water-anionic surfactant system

Surfactants can be added to pesticide-contaminated soils to enhance the treatment efficiency of soil washing. Our results showed that pesticide (atrazine and diuron) partitioning and desorbability within a soil-water-anionic surfactant system is soil particle-size dependent and is significantly influenced by the presence of anionic surfactant. Anionic surfactant (linear alkylbenzene sulphonate, LAS) sorption was influenced by its complexation with both the soluble and exchangeable divalent cations in soils (e.g. Ca²⁺, Mg²⁺). In this study, we propose a new concept: soil system hardness which defines the total amount of soluble and exchangeable divalent cations associated with a soil. Our results showed that anionic surfactant works better with soils having lower soil system hardness. It was also found that the hydrophobic organic compounds (HOCs) sorbed onto the LAS-divalent cation precipitate, resulting in a significant decrease in the aqueous concentration of HOC. Our results showed that the effect of exchangeable cations and sorption of HOC onto the surfactant precipitates needs to be considered to accurately predict HOC behavior within soil-water-anionic surfactant systems.     

Effect of cow slurry amendment on atrazine dissipation and bacterial community structure in an agricultural Andisol

Atrazine is a commonly used herbicide for maize production in Chile, but it has recently been shown to be ineffective in soils that receive applications of cow slurries generated from the dairy industry. This effect may be caused either by the sorption of the pesticide to organic matter or more rapid degradation in slurry-amended soils. The objectives of this study were to evaluate the effects of cow slurry on atrazine dissipation, the formation of atrazine metabolites and the modification of bacterial community in Andisol. The cow slurry was applied at doses of 100,000-300,000 L ha^− 1. After 4 weeks, atrazine was applied to the slurry-amended soils at concentrations of 1-3 mg kg^− 1. The amounts of atrazine and its metabolites were determined by high performance liquid chromatography (HPLC). The soil microbial community was monitored by measurement of CO₂ evolution and changes in bacterial community using PCR-DGGE of 16S rRNA genes. The results show that cow slurry applications had no effect on atrazine dissipation, which had a half-life of 15-19 days. The atrazine metabolites were detected after 20 days and were significantly higher in soils amended with the slurry at both 20 and 40 days after application of the herbicide. Respiration rates were elevated after 10 days in all soils with atrazine addition. Both the atrazine and slurry amendments altered the bacterial community structures, indicated by the appearance of specific bands in the DGGE gels after 10 days. Cloning and sequencing of the 16S rRNA genes from the DGGE gels showed that the bands represented various genera of β-proteobacteria that appeared in response to atrazine. According to our results, further field studies are required to explain the lower effectiveness of atrazine in weed control. These studies may include the effect of dissolved organic carbon on the atrazine mobility.     

Assessment of olive cake as soil amendment for the controlled release of triazine herbicides

Organic matter-rich agricultural by-products are being produced in huge quantities and can be applied to soil as a disposal strategy. The application of two different rates (2 and 8% w/w) of olive cake to a Mediterranean calcareous soil resulted in an increased sorption of four triazine herbicides, which was higher for the more hydrophobic compounds (terbuthylazine and prometryn) and lower for the more polar ones (simazine and cyanazine). However, when the sorption coefficients were normalised to the total soil organic carbon (K(oc)), the results did not significantly differ between simazine and cyanazine which is an indication that the olive cake did not exert different sorption capacity for both compounds. On the contrary, K(oc) values for terbuthylazine and prometryn increased in the amended soils. Our results from experiments using mixtures of several pesticides suggest that competition for sorption sites resulted in a decrease of herbicide sorption. Desorption was hysteretical both for the amended and unamended soils, but the addition of olive cake at the highest dose diminished desorption of most of the herbicides. In conclusion, the addition of olive cake behaves as a promising method for reducing the risk of groundwater pollution by pesticides.     

Fate and transport of 1278-TCDD, 1378-TCDD, and 1478-TCDD in soil-water systems

The most toxic dioxin is 2,3,7,8-tetrachlorodibenzo-p-dioxin (2378-TCDD), and obtaining comprehensive experimental data for this compound is challenging. However, several nontoxic isomers of 2378-TCDD exist, and can provide significant experimental evidence about this highly toxic dioxin. The goal of this study was to obtain experimental evidence for the fate and transport of 2378-TCDD in natural soils using its nontoxic isomers, 1,2,7,8-tetrachlorodibenzo-p-dioxin (1278-TCDD), 1,3,7,8-tetrachlorodibenzo-p-dioxin (1378-TCDD), and 1,4,7,8-tetrachlorodibenzo-p-dioxin (1478-TCDD). Batch sorption and miscible-displacement experiments, in various soils, were done using [4-(14)C]-radiolabeled TCDDs, while metabolism of these compounds was monitored. The results from the batch experiments indicated a high sorption affinity of all the TCDD isomers to soils and a strong correlation to organic matter (OM) content. 1278-TCDD, 1378-TCDD and 1478-TCDD (TCDDs) were more tightly bound to the soil with high OM than to the soil with low OM; however, it took a longer contact time to approach sorption equilibrium of TCDDs in the soil with high OM. Miscible-displacement breakthrough curves indicated chemical nonequilibrium transport, where there was a rate-limited or kinetic sorption that was likely caused by OM. Combustion analyses of extracted soil from the soil columns showed that most TCDDs were adsorbed in the top 1-5 cm of the column. These column combustion results also showed that sorption was correlated to specific surface and soil depth, which suggested the possibility of colloidal transport.     

Impact of soil-chemical interactions on the bioavailability of naphthalene and 1-naphthol

The bioavailability of sorbed naphthalene and 1-naphthol was determined for two sandy soils differing primarily in organic matter content. Different sorption conditions were maintained over a 2 d equilibration period to estimate the extent that oxidative coupling contributed to the strong binding of these compounds to the soils. Weakly sorbed test compounds were removed through 50 successive water extractions and the bioavailability of the remaining sorbed fraction was determined by the addition of aerobic, test compound-degrading bacteria to soil slurry reactors. Soils were then incubated under aerobic conditions for 90 d. Biodegradation rates were determined by monitoring ¹⁴CO₂ evolution and the soil-associated non-mineralized residue was measured by combustion of the soil after the 90 d period. Successive water extractions removed 38.7–64.3% of 1-naphthol and 62.4% of naphthalene from the high NOM soil and 67.2–82.9% of 1-naphthol and 72.3% of naphthalene from the low NOM soil. Of the remaining material, 5.7–16.9% of 1-naphthol and 73.3% of naphthalene in the high NOM soil and 3.7–6.0% of 1-naphthol and 34.2% of naphthalene in the low NOM soil was mineralized after 90 d. In contrast, >85% of both test compounds were mineralized in the absence of soil. Experimental evidence suggests that oxidative coupling reactions limited the bioavailability of 1-naphthol in both soils. Naphthalene bioavailability was not greatly limited because it can not directly participate in strong binding reactions.     

Binding and mobility of mercury in soils contaminated by emissions from chlor-alkali plants

Chlor-alkali plants are known to be an important source of Hg emissions to the atmosphere and related contamination of soils in their vicinity. In the present study, the results of Hg speciation and mobility of Hg in soils affected by Hg emissions from three chlor-alkali plants are compared. Solid phase mercury speciation analyses was carried out using a mercury-thermo-desorption technique with the aim of distinguishing elemental Hg [Hg(0)] from Hg(II)-binding forms. Mercury species in soil leachates were distinguished using an operationally defined method, which is based on the reactivity of soluble Hg compounds. Results show that the Hg(0) emitted from the plants could not be detected in any of the investigated soils. This indicates quantitative re-emission or oxidation of this Hg species in the atmosphere or soils. In most soils Hg was predominately bound to organic matter. Only in sandy soils deficient in organic matter was Hg, to a larger extent, sorbed onto mineral soil components. Leachable Hg in most soils occurred as non-reactive, soluble organic Hg complexes such as fulvic acid-bound Hg, and reach their highest values (90 microg kg(-1)) in soils rich in organic matter. Concentrations of reactive, soluble Hg compounds were highest in sandy soils where the content of organic matter was low. Leachability of Hg was found to be inhibited in soils with a high content of clayey soil components. The distribution of Hg in soil profiles suggests that migration of Hg to deeper soil layers (approx. 20 cm) is most effective if Hg is bound to soluble organic complexes, whereas reactive Hg or weak Hg complexes are effectively retained in the uppermost soil layer (5 cm) through sorption on mineral surfaces.     

Mobilization of arsenic by dissolved organic matter from iron oxides, soils and sediments

The arsenic contamination of aquifers has been linked to the input of dissolved organic matter (DOM). In light of this suggestion, the aim of this study was to quantify chemical effects of DOM on desorption and redox transformations of arsenic bound to synthetic iron oxide and natural samples from different geochemical environments (soils, shallow aquifer, lake sediment). In batch experiments, solutions containing 25-50 mg/L of two different types of DOM (purified peat humic acid and DOM from a peat drainage) were used as extractants in comparison to inorganic solutions. DOM solution was able to mobilize arsenic from all solid phases. Mobilization from iron oxides (maximum: 53.3%) was larger than from natural samples (maximum: 2.9%). The mobilization effect of extractants decreased in the order HCl>NaH2PO4>DOM>NaNO3. DOM solutions, therefore, mainly targeted weakly sorbed arsenic. Mobilization was complete within 24-36 h and DOM was sorbed during incubation indicating competition for sorption sites. The same patterns were observed for different DOM types and concentrations. Addition of DOM lead to (a) enhanced reduction (maximum 7.8%) and oxidation (6.4%) of arsenic in aqueous solution and (b) the appearance of arsenite in aqueous phase of soil samples (5.5%). As the primary mechanism for the arsenic release from solid phases we identified the competition between arsenic and organic anions for sorption sites, whereas redox reactions were probably of minor importance. The results of this study demonstrate that sorption of DOM has a strong potential to mobilize arsenic from soils and sediments.     

Aqueous chemistry and interactive effects on non-ionic surfactant and pentachlorophenol sorption to soil

Non-ionic surfactant addition was investigated as a method to remediate pentachlorophenol (PCP) contaminated soil. The goal was to quantify surfactant (Tergitol NP-10 (TNP10)) and PCP sorption to soil and their interactive effects under varying pH, ionic strength, and soil conditions. Up to 16,700 mg/kg of TNP10 partitioned to soil, with increasing sorption far above the critical micelle concentration (CMC) and with greater amounts of PCP present. Approximately 40-45 times more TNP10 and 20-30 times more PCP sorbed to the finer soil with higher organic matter content. Aqueous TNP10 concentrations well above the CMC (>/=5500 mg/L) were required to enhance PCP desorption from the soil. As pH increased by 0.5-0.85 units, TNP10 sorption decreased by 14-25% and PCP sorption as measured by the log of the equilibrium partition coefficient decreased by 1-1.5. A lower ionic strength of 0.03 versus 0.112 M increased PCP desorption from contaminated soil by 5-17% in the presence of TNP10. This work is relevant to designing ex situ soil washing or surfactant-aided PCP remediation.     

Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: effects of sorption, surfactants, and natural organic matter

Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1×cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the presence of SDS at sub-cmc increased TCE degraded by ∼10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5×cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe-Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses.     

Occurrence and load of selected herbicides and metabolites in the lower Mississippi River

Analyses of water samples collected from the Mississippi River at Baton Rouge, Louisiana, during 1991-1997 indicate that hundreds of metric tons of herbicides and herbicide metabolites are being discharged annually to the Gulf of Mexico. Atrazine, metolachlor, and the ethane-sulfonic acid metabolite of alachlor (alachlor ESA) were the most frequently detected herbicides and, in general, were present in the largest concentrations. Almost 80% of the annual herbicide load to the Gulf of Mexico occurred during the growing season from May to August. The concentrations and loads of alachlor in the Mississippi River decreased dramatically after 1993 in response to decreased use in the basin. In contrast, the concentrations and loads of acetochlor increased after 1994, reflecting its role as a replacement for alachlor. The peak annual herbicide load occurred in 1993, when approximately 640 metric tons (t) of atrazine, 320 t of cyanazine, 215 t of metolachlor, 53 t of simazine, and 50 t of alachlor were discharged to the Gulf of Mexico. The annual loads of atrazine and cyanazine were generally 1-2% of the amount annually applied in the Mississippi River drainage basin; the annual loads of acetochlor, alachlor, and metolachlor were generally less than 1%. Despite a reduction in atrazine use, historical data do not indicate a long-term downward trend in the atrazine load to the Gulf of Mexico. Although a relation (r2 = 0.62) exists between the atrazine load and stream discharge during May to August, variations in herbicide use and rainfall patterns within subbasins can have a large effect on herbicide loads in the Mississippi River Basin and probably explain a large part of the annual variation in atrazine load to the Gulf of Mexico.     

Sorption of phenols to dissolved organic matter investigated by solid phase microextraction

The sorption of phenol and different halogenated phenols to natural organic matter of a brown water lake (HO14), of a compost extract, of Aldrich humic acid (Aldrich-HA), and to the protein bovine serum albumin (BSA) was investigated using solid phase microextraction (SPME). The limit of determination for the SPME analysis was < 15 microg/l for all phenols investigated. The extraction coefficients K(F) were calculated according to a first-order extraction kinetics. In general, the extraction equilibrium was established faster due to the presence of dissolved organic matter (DOM). The highest sorption capacity of phenols was observed for BSA with log K(OC) values in the range between 2 and 6. For the compost extract and HO14 only a small sorption of the investigated phenols was determined. On the other hand, Aldrich humic acid showed a reasonable sorption of phenols with log K(OC) values between 2 and 3. The sorption to DOM decreased when the pH of the solution was increased.