Compost and vermicompost of olive cake to bioremediate triazines-contaminated soil

The use of organic amendments to bioremediate potential organic pollutants of soil and water has become an increasingly relevant issue in the last years. This strategy has been applied to four triazine herbicides in a typical calcareous agricultural soil of the Mediterranean area. The soil was amended with olive cake, compost and vermicompost of olive cake at rates four times higher than the agronomic dose in order to stimulate biodegradation of simazine, terbuthylazine, cyanazine and prometryn, added in a mixture to the soils. Degradation studies were carried out in sterile and microbially active soil to evaluate the effect of the chemical and biological degradation of triazines. The residual herbicide concentrations at the end of the degradation assay showed no significant differences between non amended and amended soil. However, the addition of compost and vermicompost enhanced the biological degradation rate of triazines during the first week of incubation, with half-lives ranging form 5 to 18 days for the amended soils, whilst negligible degradation occurred in non-amended soil during this period. In contrast, olive cake did not significantly modify the degradation of triazines in spite that the addition of this amendment to soil resulted in the highest dehidrogenase activity values. In all the substrates, degradation of cyanazine and prometryn was faster (between 1.5 and two times higher) than those of terbuthylazine and simazine, without significant relationship with sorption parameters. The first order kinetic equation satisfactorily explained the experimental data for all triazines. A biphasic model, such as that proposed by Hoerl, was better to predict the very rapid triazines decay during the first week of incubation in soil amended with compost and vermicompost.     

Persistence of four s-triazine herbicides in river, sea and groundwater samples exposed to sunlight and darkness under laboratory conditions

The persistence of terbuthylazine, simazine, atrazine and prometryn (s-triazine herbicides) was studied in sea, river and groundwaters during long-term laboratory incubation (127 days) under different laboratory conditions (light-darkness at 20 degrees C). Analysis of herbicides was performed by GC-NPD and their identity was confirmed by GC-MSD. A micro on-line method for the isolation of herbicide residues was used. The results showed that light had little effect on the removal of the four herbicides in riverwater but had a marked effect on their removal from sea and groundwater. Surprisingly, this removal appeared to be inversely proportional to the concentration of dissolved organic materials. In general, the degradation order was similar in sea and riverwaters; simazine was the most readily degraded compound (t(1/2)= 29-49 days), while terbuthylazine was the most persistent with the longest half-lives (76-331 days). In groundwater, terbuthylazine also showed greater persistence but prometryn was the compound with a fastest degradation rate, half-lives ranged from 88 days for prometryn to approximately 100 days for the other three compounds in light conditions and 263-366 days for prometryn and terbuthylazine, respectively, in darkness. Only for terbuthylazine was the remaining percentage at the end of the experiment higher than 50% under light conditions in riverwater, while in the other cases, the remaining percentage varied from 7 to 43% for simazine in seawater and atrazine in groundwater, respectively. Finally, a greater persistence was observed in groundwater for the four compounds.     

Application of a GIS-AF/RF model to assess the risk of herbicide leaching in a citrus-growing area of the Valencia Community, Spain

We integrated an index-based attenuation factor/retardation factor (AF/RF) model into a GIS to evaluate the risk of leaching of the most frequently applied herbicides (glyphosate, diuron, diquat, bromacil, simazine, linuron, terbuthylazine, and terbumeton) used in citrus orchards of the Valencia Community, Spain. The GIS-model system was applied to a region of 33,800 ha located near Valencia City. The soil and climate data required by the model were stored in an Arc/Info GIS in which the model algorithms were integrated using the AML programming language. A graphical user interface was developed to facilitate the use of the GIS-model system. The resulting simulation maps indicate that terbumeton, bromacil, and simazine herbicides have the highest risk of leaching because of their high mobility and low K(oc) (32-158 mg l(-1)). The remaining herbicides are strongly adsorbed by clay particles and organic matter, thus minimising the risk of leaching through the soil profile and into groundwater. The obtained ranking of the leaching potential of analysed herbicides is as follows, from highest to lowest risk: terbumeton>bromacil>simazine>terbuthylazine>diuron>linuron>glyphosate>diquat.     

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.     

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.     

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.     

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 chemicals (HOC) into anionic and cationic surfactant-modified sorbents

Surfactant-modified sorbents have been proposed for the removal of organic compounds from aqueous solution. In the present study, one cationic (HDTMA) and three anionic (DOWFAX-8390, STEOL-CS330, and Aerosol-OT) surfactants were tested for their sorptive behavior onto different sorbents (alumina, zeolite, and Canadian River Alluvium). These surfactant-modified materials were then used to sorb a range of hydrophobic organic chemicals (HOCs) of varying properties (benzene, toluene, ethylbenzene, 1,2-dichlorobenzene, naphthalene, and phenanthrene), and their sorption capacity and affinity (organic-carbon-normalized sorption coefficient, K(oc)) were quantified. The HDTMA-zeolite system proved to be the most stable surfactant-modified sorbent studied because of the limited surfactant desorption. Both anionic and cationic surfactants resulted in modified sorbents with higher sorption capacity and affinity than the unmodified Canadian River Alluvium containing only natural organic matter. The affinities of the surfactant-modified sorbents (K(oc)) for most HOCs are lower than octanol/water partition coefficient (K(ow)) normalized to the organic carbon content (f(oc)) and the density of octanol (K(oc) octanol); naphthalene and phenanthrene are the exceptions to this rule.     

Evaluating phenanthrene sorption on various wood chars

A certain amount of wood char or soot in a soil or sediment sample may cause the sorption of organic compounds to deviate significantly from the linear partitioning commonly observed with soil organic matter (SOM). Laboratory produced and field wood chars have been obtained and analyzed for their sorption isotherms of a model solute (phenanthrene) from water solution. The uptake capacities and nonlinear sorption effects with the laboratory wood chars are similar to those with the field wood chars. For phenanthrene aqueous concentrations of 1 microg l(-1), the organic carbon-normalized sorption coefficients (log K(oc)) ranging from 5.0 to 6.4 for field chars and 5.4-7.3 for laboratory wood chars, which is consistent with literature values (5.6-7.1). Data with artificial chars suggest that the variation in sorption potential can be attributed to heating temperature and starting material, and both the quantity and heterogeneity of surface-area impacts the sorption capacity. These results thus help to corroborate and explain the range of logK(oc) values reported in previous research for aquifer materials containing wood chars.     

The influence of N load and harvest intensity on the risk of P limitation in Swedish forest soils

Field burning of crop residue is a common post-harvest practice to dispose of these agricultural by-products and for land clearing. Burned crop residues may effectively adsorb pesticides and thus influence their bioavailability in agricultural soils. The adsorption of clomazone by a soil amended with a burned rice straw (BRS) was measured. The availability of clomazone to barnyardgrass in the soil in the absence and presence of BRS was tested. The BRS was 1000-20,000 times more effective than soil in sorbing clomazone. The sorption of clomazone by soil increased with increasing BRS amount in the soil. In a bioassay, the injury of barnyardgrass 9 days after planting decreased with increasing BRS amount in soil indicating the effect of BRS on clomazone availability. Residual analyses showed higher concentrations of clomazone in soils receiving higher rates of the herbicide than in soils with lower application rates suggesting the adsorptive role of BRS. At typical application rate of clomazone (0.3 microg g(-1)), BRS amounts of 0.02 wt.% and higher caused an appreciable reduction to a complete loss in clomazone availability. Calculations suggest that field burning of rice straw may result in sufficiently high amounts (>0.02 wt.%) of BRS, and hence contribute to often experienced loss of pesticide availability in agricultural soils. Our results may be extended to field situations where other crop residues and vegetation are burned. Alternative management of crop residues may improve the bioavailability of pesticides in agricultural soils.     

Use of solvents to enhance PAH biodegradation of coal tar-contaminated soils

Bioremediation of coal tar-contaminated soils containing polycyclic aromatic hydrocarbons (PAHs) is highly challenging because of the low solubility and strong sorption properties of PAHs. Five coal tar-contaminated soils from former manufactured gas plant (MGP) sites were pretreated with two solvents, acetone and ethanol to enhance the bioavailability of the PAH compounds. The biodegradation of various PAHs in the pretreated soils was assessed using soil slurry reactors. The total PAH degradation rates for soils pretreated with solvents were estimated to be about two times faster than soils that were not pretreated with solvents. For example, the total PAH first order degradation rate constants were 0.165+/-0.032, 0.147+/-0.020, and 0.076+/-0.009 day(-1) for Vandalia (EXC) soil that were pretreated with acetone, ethanol, and with no solvent, respectively. A distinctive advantage for soils pretreated with solvents was the enhanced removal of 5-ring PAH compounds such as benzo(a)pyrene and to a limited extent 4-ring compounds such as chrysene. Even for soils with 3.5% or more organic carbon content (two soils out of five), the degradation rate constants of chrysene were found to be two times faster than soils that were not pretreated. The degradation rate constants of benzo(a)pyrene were enhanced by 2-6 times for all five contaminated soils that were pretreated with solvents. To further elucidate trends that control the solvent treatment, the percent improvement in degradation rate constants (100 x rate constants for pretreated soils/rate constants for non-treated soils) for 16 PAHs were found to correlate well with the PAH partition coefficients (K(oc)). Except for phenanthrene and the clay fraction of the soil, correlations between the percent improvement in degradation rates constants and several physical properties of the soils were poor and sporadic. This implies that the enhancement in PAH availability using solvent treatment was driven by the distribution of the PAHs between the solvent and the adsorbed PAHs.     

Removal of pesticide mixtures in a stormwater wetland collecting runoff from a vineyard catchment

Wetlands can collect contaminated runoff from agricultural catchments and retain dissolved and particle-laden pesticides. However, knowledge about the capacity and functioning of wetland systems with respect to the removal of pesticides is very limited. Here we show that stormwater wetlands can efficiently remove pesticides in runoff from vineyard catchments during the period of pesticide application, although flow and hydrochemical conditions of the wetland largely vary over time. During the entire agricultural season, the inflowing load of nine fungicides, six herbicides, one insecticide and four degradation products was 8.039 g whereas the outflowing load was 2.181 g. Removal rates of dissolved loads by the wetland ranged from 39% (simazine) to 100% (cymoxanil, gluphosinate, kresoxim methyl and terbuthylazine). Dimethomorph, diuron, glyphosate, metalaxyl and tetraconazole were more efficiently removed in spring than in summer. More than 88% of the input mass of suspended solids was retained, underscoring the capability of the wetland to trap pesticide-laden particles via sedimentation. Only the insecticide flufenoxuron was frequently detected in the wetland sediments. Our results demonstrate that stormwater wetlands can efficiently remove pesticide mixtures in agricultural runoff during critical periods of pesticide application, although fluctuations in the runoff regime and hydrochemical characteristics can affect the removal rates of individual pesticides.     

Pesticides in Portuguese surface and ground waters

Pesticides used in Portuguese agricultural areas have been found in surface and ground waters. In the surface water collected in three river basins from 1983 to 1999, insecticides and herbicides were detected from the monitored pesticides, particularly atrazine, chlorfenvinphos (Z+E), alpha- and beta-endosulfan, lindane, molinate and simazine, reaching the maximum values, respectively, of 0.63, 31.6, 0.18 microg/L (alpha-endosulfan), 0.18 microg/L (beta-endosulfan), 0.24, 48 and 0.3 microg/L. In the ground water collected from the wells of seven agricultural areas from 1991 to 1998, several monitored herbicides were detected: alachlor, atrazine, metolachlor, metribuzine and simazine, reaching the maximum concentration values of 13, 30, 56, 1.4 and 0.4 microg/L, respectively. The herbicides more frequently detected were atrazine (64%), simazine (45%) and alachlor (25%). Other than these, the monitored pesticides can be present in Portuguese surface and ground waters. Therefore, to improve the analytical conditions, the use of multiresidue methods and automated techniques are desirable in future work.     

Occurrence of cotton herbicides and insecticides in playa lakes of the High Plains of West Texas

During the summer of 1997, water samples were collected and analyzed for pesticides from 32 playa lakes of the High Plains that receive drainage from both cotton and corn agriculture in West Texas. The major cotton herbicides detected in the water samples were diuron, fluometuron, metolachlor, norflurazon, and prometryn. Atrazine and propazine, corn and sorghum herbicides, were also routinely detected in samples from the playa lakes. Furthermore, the metabolites of all the herbicides studied were found in the playa lake samples. In some cases, the concentration of metabolites was equal to or exceeded the concentration of the parent compound. The types of metabolites detected suggested that the parent compounds had been transported to and had undergone degradation in the playa lakes. The types of metabolites and the ratio of metabolites to parent compounds may be useful in indicating the time that the herbicides were transported to the playa lakes. The median concentration of total herbicides was 7.2 microg/l, with the largest total concentrations exceeding 30 microg/l. Organophosphate insecticides were detected in only one water sample. Further work will improve the understanding of the fate of these compounds in the playa lake area.     

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.     

The Translocation of Some Herbicides between Soil and Water in a Small Catchment

This paper presents data on the distribution of four herbicides within an agricultural catchment. In the case of mecoprop, 2,4-dichlorophenoxyacetic acid and simazine, these data include concentrations in the soil, field drains and the stream, before and after applications of the herbicides following good agricultural practice. The concentrations of these herbicides in the soil were found to follow published degradation rates, and their concentrations in the stream and drains were elevated following rainfall with peak concentrations from 0.12 μg/1 to 68.0 μg/1. Atrazine was found at relatively high concentrations (peak 122 μg/1) when it had not been applied to any of the fields draining to the sampling point.
The data will be used to test models that may be used as one of a number of tools for the screening of new pesticides prior to their registration. One approach using the Mackay's fugacity model is outlined.     

Field tests of surface seals and soil treatments to reduce fumigant emissions from shank injection of Telone C35

A mixture of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) (Telone C35) is an increasingly used fumigant product for pre-plant soil fumigation in California, USA. Atmospheric emissions of volatile organic compounds, including these important pesticides, is more heavily regulated in an effort to improve air-quality. Research has identified various methods of reducing fumigant emissions but effective and economically feasible field methods are still needed. The objective of this field study was to determine the effectiveness of several surface seal and soil treatment methods on emissions of 1,3-D and CP from shank-injected Telone C35. Treatments included control (bare surface), pre-irrigation (irrigation prior to fumigation), post-fumigation water seals with or without potassium thiosulfate (KTS) amendment, and standard high density polyethylene (HDPE) tarp over soils amended with either KTS or composted manure. The two KTS treatments resulted in the lowest fumigant emissions; but the soil surface in the treatments developed a reddish-orange color and an unpleasant odor that lasted for a few months. The pre-irrigation reduced emissions more than post-application water seals. An application of composted manure at 12.4 Mg ha(- 1) spread over the soil surface followed by HDPE tarp did not reduce 1,3-D emissions compared to the bare soils in this trial, indicating that a better understanding of processes is required in order to effectively use organic amendments for minimizing fumigant emissions. Chloropicrin emissions were generally lower than 1,3-D for all treatments.     

Field trials to assess the use of iron-bearing industrial by-products for stabilisation of chromated copper arsenate-contaminated soil

Two industrial by-products with high iron contents were tested for their effectiveness in the stabilisation of arsenic and trace metals in chromated copper arsenate (CCA)-contaminated soil. Steel abrasive (SA; 97% Fe(0)) and oxygen scarfing granulate (OSG; 69% Fe(3)O(4)) were applied at levels of 1% and 8% (w/w) respectively to two soils with different organic matter contents. Field lysimeter measurements indicated that SA and OSG treatments decreased the arsenic concentration in pore water by 68% and 92%, respectively, for the soil with low organic matter content, and by about 30% in pore water of soil with high organic matter content. At pH < or =6, the amended soil with low organic content contained elevated levels of manganese and nickel in their pore water, which were sufficient to induce cytotoxic effects in L-929 mouse fibroblast cells. The industrial by-products have significant potential for soil amendment at field-scale, but caution is required because of the potential release of their chemical contaminants and their reduced capacity for sorption of arsenic in organic-rich soils.     

Distributions of polycyclic aromatic hydrocarbons in surface waters, sediments and soils of Hangzhou City, China

Ten polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in 17 surface water samples and 11 sediments of four water bodies, and 3 soils near the water-body bank in Hangzhou, China in December 2002. It was observed that the sum of PAHs concentrations ranged from 0.989 to 9.663 microg/L in surface waters, from 132.7 to 7343 ng/g dry weight in sediments, and from 59.71 to 615.8 ng/g dry weight in soils. The composition pattern of PAHs by ring size in water, sediment and soil were surveyed. Three-ring PAHs were dominated in surface waters and soils, meanwhile sediments were mostly dominated by four-ring PAHs. Furthermore, PAHs apparent distribution coefficients (K(d)) and solid f(oc)-normalized K(d) (e.g. K(oc)= K(d) / f(oc)) were calculated. The relationship between logK(oc) and logK(ow) of PAHs for field data on sediments and predicted values were compared. The sources of PAHs in different water bodies were evaluated by comparison of K (oc) values in sediments of the river downstream with that in soils. Hangzhou section of the Great Canal was heavily polluted by PAHs released from industrial wastewater in the past and now PAHs in sediment may serve as sources of PAHs in surface water. PAHs in Qiantang River were contributed from soil runoff. Municipal road runoff was mostly contributed to West Lake PAHs.     

Remediation of waters contaminated with ionic herbicides by sorption on polymerin

This study investigated the sorption of paraquat and 2,4-D on polymerin, the humic acid-like fraction of olive mill wastewater. Effects of pH, contact time, initial concentration and sorbent dosage on the sorption of both herbicides were studied. The sorption mechanism of paraquat on polymerin was consistent with the ion exchange of this herbicide with Ca, Mg and K natively occurring in the sorbent; in contrast, 2,4-D was bound to polymerin by hydrogen bonding. Simulated wastewaters contaminated with paraquat were purified after three sorption cycles on polymerin renewed at each cycle, at a solid/liquid ratio of 0.5, whereas those containing 2,4-D showed a maximal residue removal of 44% after two sorption cycles at the same ratio. The possible application of this model to other water-soluble herbicides, as well as the possible exploitation of polymerin as a bio-filter for the decontamination of pollution point sources is briefly discussed.