Size distribution of organic matter and associated propiconazole in agricultural runoff material

Sorption and desorption characteristics of propiconazole (1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole) to different particle/aggregate-size fractions of agricultural runoff material were investigated. Emphasis was put on clay and colloidal size fractions to evaluate their role as potential sorbents and carriers for this pesticide. The runoff material was separated into size fractions ranging from 2 mm to ca. 15 nm by wet sieving, sedimentation, centrifugation, and membrane ultrafiltration. Each fraction was characterized by its organic C content and C/N ratio. Distinctive sorption properties of clay-sized particles and colloids were investigated. The obtained size fractions differed significantly in their organic C concentration, C/N ratio, and sorption properties to propiconazole. Organic matter was mainly associated in aggregates >2 microm. Binding of propiconazole to this coarse fraction made up 80% of the sorbed propiconazole. The distribution coefficient between solid and aqueous phases increased with decreasing particle size. The colloidal fraction (<0.16 microm) exhibited the highest sorbtivity, with a distribution coefficient of 113 L kg(-1), which was more than four times higher than that in the bulk sample (27 L kg(-1)). The fraction <2 microm represented 8% of the total sample weight, but contributed to 20% of the sorbed propiconazole. Strong hysteresis was observed for the sorption-desorption of propiconazole on the runoff material. Under dilution very little sorbed propiconazole will be released into the water phase. Due to its high sorbtivity and mobility and the strong sorption-desorption hysteresis, particles in the fraction <2 microm can be important carriers of propiconazole in runoff suspensions with high sediment load.     

THE SUSPENDED SEDIMENT REGIME OF AN OREGON COAST RANGE STREAM1

ABSTRACT: Armored stream segments may affect the suspended sediment regime of small mountain streams in western Oregon by the release of fine sediments stored in the bed gravels. Sieve analysis of bed materials indicated that at least 30 percent of the suspended sediment yield for the 1975–76 winter had been stored in the streambed. Suspended sediment concentrations during storm-generated runoff were influenced by stream discharge and hydrograph characteristics. Sediment-discharge relations for individual storms were characterized by hysteresis loops. A seasonal flushing of fines was shown by a progressive decrease in the ratio of suspended sediment to stream discharge during the winter runoff period.     

Three-dimensional numerical simulation of water quality and sediment-associated processes with application to a Mississippi Delta lake

A three-dimensional water quality model was developed for simulating temporal and spatial variations of phytoplankton, nutrients, and dissolved oxygen in freshwater bodies. Effects of suspended and bed sediment on the water quality processes were simulated. A formula was generated from field measurements to calculate the light attenuation coefficient by considering the effects of suspended sediment and chlorophyll. The processes of adsorption–desorption of nutrients by sediment were described using the Langmuir Equation. The release rates of nutrients from the bed were calculated based on the concentration gradient across the water–sediment interface and other variables including pH, temperature and dissolved oxygen concentration.The model was calibrated and validated by applying it to simulate the concentrations of chlorophyll and nutrients in a natural oxbow lake in Mississippi Delta. The simulated time series of phytoplankton (as chlorophyll) and nutrient concentrations were generally in agreement with field observations. Sensitivity analyses were conducted to demonstrate the impacts of varying suspended sediment concentration on lake chlorophyll levels.     

Sorption-desorption of carbamazepine from irrigated soils

Th anti-seizure medication carbamazepine is often found in treated sewage effluent and environmental samples. Carbamazepine has been shown to be very persistent in sewage treatment, as well as ground water. Due to environmental persistence, irrigation with sewage effluent could result in carbamazepine contamination of surface and ground water. To determine the potential for leaching of carbamazepine, a series of adsorption and desorption batch equilibrium experiments were conducted on irrigated soils. It was found that carbamazepine adsorption to biosolid-amended (T) soils had a KD of 19.8 vs. 12.6 for unamended soil. Based on adsorption, carbamazepine leaching potential would be categorized as low. During desorption significant hysteresis was observed and KD increased for both soils. Desorption isotherms also indicate a potential for irreversibly bound carbamazepine in the T soil. Results indicate that initial removal of carbamazepine via adsorption from irrigation water is significant and that desorption characteristics would further limit the mobility of carbamazepine through the soil profile indicating that carbamazepine found in sewage effluent used for irrigation has a low leaching potential.     

Sorption and degradation of pesticides in nursery recycling ponds

Knowledge of pesticide distribution and persistence in nursery recycling pond water and sediment is critical for preventing phytotoxicity of pesticides during water reuse and to assess their impacts to the environment. In this study, sorption and degradation of four commonly used pesticides (diazinon, chlorpyrifos, chlorothalonil, and pendimethalin) in sediments from two nursery recycling ponds was investigated. Results showed that diazinon and chlorothalonil were moderately sorbed [K(OC) (soil organic carbon distribution coefficient) from 732 to 2.45 x 10(3) mL g(-1)] to the sediments, and their sorption was mainly attributable to organic matter content, whereas chlorpyrifos and pendimethalin were strongly sorbed (K(OC) > or = 7.43 x 10(3) mL g(-1)) to the sediments, and their sorption was related to both organic matter content and sediment texture. The persistence of diazinon and chlorpyrifos was moderate under aerobic conditions (half-lives = 8 to 32 d), and increased under anaerobic conditions (half-lives = 12 to 53 d). In contrast, chlorothalonil and pendimethalin were quickly degraded under aerobic conditions with half-lives < 2.8 d, and their degradation was further enhanced under anaerobic conditions (half-lives < 1.9 d). The strong sorption of chlorpyrifos and pendimethalin by the sediments suggests that the practice of recycling nursery runoff would effectively retain these compounds in the recycling pond, minimizing their offsite movement. The prolonged persistence of diazinon and chlorpyrifos, however, implies that incidental spills, such as overflows caused by storm events, may contribute significant loads of such pesticides into downstream surface water bodies.     

Assessing effects of aerobic and anaerobic conditions on phosphorus sorption and retention capacity of water treatment residuals

Water treatment residuals (WTRs) are the by-products of drinking water clarification processes, whereby chemical flocculants such as alum or ferric chloride are added to raw water to remove suspended clay particles, organic matter and other materials and impurities. Previous studies have identified a strong phosphorus (P) fixing capacity of WTRs which has led to experimentation with their use as P-sorbing materials for controlling P discharges from agricultural and forestry land. However, the P-fixing capacity of WTRs and its capacity to retain sorbed P under anaerobic conditions have yet to be fully demonstrated, which is an issue that must be addressed for WTR field applications. This study therefore examined the capacity of WTRs to retain sorbed P and sorb further additional P from aqueous solution under both aerobic and anaerobic conditions. An innovative, low cost apparatus was constructed and successfully used to rapidly establish anoxic conditions in anaerobic treatments. The results showed that even in treatments with initial solution P concentrations set at 100 mg l(-1), soluble reactive P concentrations rapidly fell to negligible levels (due to sorption by WTRs), while total P (i.e. dissolved + particulate and colloidal P) was less than 3 mg l(-1). This equated to an added P retention rate of >98% regardless of anaerobic or aerobic status, indicating that WTRs are able to sorb and retain P in both aerobic and anaerobic conditions.     

Sorption and desorption of cadmium by different fractions of biosolids-amended soils

To evaluate the importance of both the inorganic and organic fractions in biosolids on Cd chemistry, a series of Cd sorption and desorption batch experiments (at pH 5.5) were conducted on different fractions of soils from a long-term field experimental site. The slope of the Cd sorption isotherm increased with rate of biosolids and was different for the different biosolids. Removal of organic carbon (OC) reduced the slope of the Cd sorption isotherm but did not account for the observed differences between biosolids-amended soils and a control soil, indicating that the increased adsorption associated with biosolids application was not limited to the increased OC from the addition of biosolids. Removal of both OC and Fe/Mn further reduced the slopes of Cd sorption isotherms and the sorption isotherm of the biosolids-amended soil was the same as that of the control, indicating both OC and Fe/Mn fractions added by the biosolids were important to the increased sorption observed for the biosolids-amended soil samples. Desorption experiments failed to remove from 60 to 90% of the sorbed Cd. This "apparent hysteresis" was higher for biosolids-amended soil than the control soil. Removal of both OC and Fe/Mn fractions was more effective in removing the observed differences between the biosolids-amended soil and the control than either alone. Results show that Cd added to biosolids-amended soil behaves differently than Cd added to soils without biosolids and support the hypothesis that the addition of Fe and Mn in the biosolids increased the retention of Cd in biosolids-amended soils.     

Assessment of spent mushroom substrate as sorbent of fungicides: influence of sorbent and sorbate properties

The capacity of spent mushroom substrate (SMS) as a sorbent of fungicides was evaluated for its possible use in regulating pesticide mobility in the environment. The sorption studies involved four different SMS types in terms of nature and treatment and eight fungicides selected as representative compounds from different chemical groups. Nonlinear sorption isotherms were observed for all SMS-fungicide combinations. The highest sorption was obtained by composted SMS from Agaricus bisporus cultivation. A significant negative and positive correlation was obtained between the K(OC) sorption constants and the polarity index values of sorbents and the K(OW) of fungicides, respectively. The statistic revealed that more than 77% of the variability in the K(OW) could be explained considering these properties jointly. The other properties of both the sorbent (total carbon, dissolved organic carbon, or pH) and the sorbate (water solubility) were nonsignificant. The hysteresis values for cyprodinil (log K(OW)= 4) were for all the sorbents much higher (>3) than for other fungicides. This was consistent with the remaining sorption after desorption considered as an indicator of the sorption efficiency of SMS for fungicides. Changes in the absorption bands of fungicides sorbed by SMS observed by FTIR permitted establishing the interaction mechanism of fungicides with SMS. The findings of this work provide evidence for the potential capacity of SMS as a sorbent of fungicides and the low desorption observed especially for some fungicides, although they suggest that more stabilized or humified organic substrates should be produced to enhance their efficiency in environmental applications.     

Adsorption of isoxaflutole degradates to aluminum and iron hydrous oxides

Isoxaflutole is a preemergence herbicide that has been marketed as a substitute for atrazine. It is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application and can further degrade to a benzoic acid degradate (BA) within soil. However, no previous research has been conducted to investigate DKN and BA sorption to metal oxide minerals. The primary objective of this research was to elucidate the interactions of DKN and BA with synthetic hydrous aluminum and iron oxides (HAO and HFO, respectively) to understand how variably charged minerals may influence adsorption of these compounds in soil. The herbicide degradates did adsorb to HAO and HFO, and the data were well described by the Freundlich model (R2 > 0.91), with Nvalues ranging from 0.89 to 1.2. Adsorption isotherms and Kd values demonstrate that BA is adsorbed to HFO to a greater extent than other degradate-mineral combinations that were studied. The degree of hysteresis between adsorption/desorption isotherms was characterized as slight (hysteresis index values < 1.7), suggesting weak DKN and BA retention to HFO and HAO oxide surfaces. Degradate adsorption was observed to greatly diminish as suspension pH increased. Attenuated total reflectance-Fourier transform infrared spectra show no evidence that DKN or BA adsorb to mineral surfaces as inner-sphere complexes under hydrated conditions. Instead DKN and BA adsorb to positively charged metal oxide surfaces as outer-sphere or diffuse ion swarm complexes via electrostatic attraction. This research indicates that metal oxides may serve as important retardants for DKN and BA migration through acidic soils enriched with aluminum and iron oxides.     

Enhanced desorption of herbicides sorbed on soils by addition of Triton X-100

A study of the desorption of atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine) and linuron [1-methoxy-1-methyl-3-(3,4-dichlorophenyl)urea] adsorbed on soils with different organic matter (OM) and clay contents was conducted in water and in the presence of the non-ionic surfactant Triton X-100 at different concentrations. The aim was to gain insight into soil characteristics in surfactant-enhanced desorption of herbicides from soils. Adsorption and desorption isotherms in water, in all Triton X-100 solutions for atrazine, and in solutions of 0.75 times the critical micelle concentration (cmc) and 1.50cmc for linuron fit the Freundlich equation. All desorption isotherms showed hysteresis. Hysteresis coefficients decreased for linuron and increased or decreased for atrazine in Triton X-100 solutions. These variations were dependent on surfactant concentration and soil OM and clay contents. In the soil-water-surfactant system desorption of linuron from all soils was always greater than in the soil-water system but for atrazine this only occurred at concentrations higher than 50cmc. For the highest Triton X-100 concentration (100cmc), the desorption of the most hydrophobic herbicide (linuron) was increased more than 18-fold with respect to water in soil with an OM content of 10.3% while the atrazine desorption was increased 3-fold. The effect of Triton X-100 on the desorption of both herbicides was very low in soil with a high clay content. The results indicate the potential use of Triton X-100 to facilitate the desorption of these herbicides from soil to the water-surfactant system. They also contribute to better understanding of the interactions of different molecules and surfaces in the complex soil-herbicide-water surfactant system.     

PROCESS-ORIENTED ESTIMATION OF SUSPENDED SEDIMENT CONCENTRATION1

ABSTRACT: Least squares regression and ARIMA models were developed from suspended sediment data for the Ausable River, Southern Ontario, Canada. A poor correlation between discharge and suspended sediment concentration results from the dynamics of the physical system, including seasonality, antecedent conditions, and hysteresis. Regression model results were significantly improved by the division of the data set into seasons and the addition of simple. but physically meaningful variables. Misleading improvements obtained from the regression of sediment load and discharge are discussed. ARIMA models provided accurate forecasts of sediment concentration on a real-time basis, but the rigorous data requirements limit their use in modeling suspended sediment concentrations in Canadian rivers.     

The role of condensed organic matter in the nonlinear sorption of hydrophobic organic contaminants by a peat and sediments

This study examines the effect of soil organic matter heterogeneity on equilibrium sorption and desorption of phenanthrene, naphthalene, 1,3,5-trichlorobenzene (1,3,5-TCB), and 1,2-dichlorobenzene (1,2-DCB) by soils and sediments. Two estuary sediments, a Pahokee peat (PP; Euic, hyperthermic Lithic Haplosaprist), and two subsamples (base- and acid-treated peat [TP] and acid-treated peat [FP]) of the peat were used as the sorbents. The contents of black carbon particles were quantified with a chemical extraction method. Petrographical examinations revealed the presence of the condensed soil and sediment organic matter (SOM) in Pahokee peat. The Freundlich isotherm model in two different forms was used to fit both sorption and desorption data. The results show that the sorption and desorption isotherms are generally nonlinear and that the apparent sorption-desorption hysteresis is present for phenanthrene and TCB. Detailed analysis of sorption data for the tested sorbent-sorbate systems indicates that black carbon is probably responsible for sorption isotherm nonlinearity for the two sediments, whereas the humic substances and kerogen may play the dominant role in nonlinear sorption by the peat. This investigation suggests that the microporosity of SOM is important for the hydrophobic organic contaminant (HOC) sorption capacity on the peat.     

Atrazine sorption-desorption hysteresis by sugarcane mulch residue

Sorption and desorption kinetics are essential components for modeling the movement and retention of applied agricultural chemicals in soils and the fraction of chemicals susceptible to runoff. In this study, we investigated the retention characteristics of sugarcane (Saccharum spp. hybrid) mulch residue for atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) based on studies of sorption-desorption kinetics. A sorption kinetic batch method was used to quantify retention of the mulch residue for a wide range of atrazine concentrations and reaction times. Desorption was performed following 504 h of sorption using successive dilutions, followed by methanol extraction. Atrazine retention by the mulch residue was well described using a linear model where the partitioning coefficient (K(d)) increased with reaction time from 10.40 to 23.4 cm3 g(-1) after 2 and 504 h, respectively. Values for mulch residue K(d) were an order of magnitude higher than those found for Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquepts) where the sugarcane crop was grown. A kinetic multireaction model was successful in describing sorption behavior with reaction time. The model was equally successful in describing observed hysteretic atrazine behavior during desorption for all input concentrations. The model was concentration independent where one set of model parameters, which was derived from all batch results, was valid for the entire atrazine concentration range. Average atrazine recovery following six successive desorption steps were 63.67 +/- 4.38% of the amount adsorbed. Moreover, a hysteresis coefficient based on the difference in the area between sorption and desorption isotherms was capable of quantifying hysteresis of desorption isotherms.     

Kinetic modeling of bioavailability for sorbed-phase 2,4-dichlorophenoxyacetic acid

The degradation rate of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in silica-slurry systems to evaluate the bioavailability of sorbed-phase contaminant. After the silica particles were saturated with 2,4-D, the system was inoculated with the 2,4-D-degrading microorganism Flavorbacterium sp. strain FB4. The disappearance rate of 2,4-D was found to be greater than the rate predicted based upon liquid-phase 2,4-D concentrations. A kinetic formulation, termed the enhanced bioavailability model, was developed to describe the desorption and biodegradation processes in this batch system. The approach assumes that 2,4-D resides in both the liquid and solid phases and degradation occurs via both suspended and attached biomass. All biomass can degrade liquid-phase 2,4-D at one rate, while only attached biomass can degrade sorbed 2,4-D at another rate. An enhanced transformation factor (Ef) was introduced to express the increased biodegradation rate over that expected from the liquid phase only. This approach was able to account for the increased degradation rates observed experimentally. The results provide evidence that desorption to the bulk solution is not prerequisite to degradation, and that sorbed substrate may be available for degradation.     

Adsorption of carbon dioxide on alkali-modified zeolite 13X adsorbents

Shaped zeolite 13X adsorbent with kaolin as binder was hydrothermally modified in sodium hydroxide solution to improve its adsorption performance. The characterization of the product by XRD, N₂ adsorption–desorption and water vapour adsorption displayed that kaolin component in zeolite adsorbent can be converted into zeolite during the alkali treatment, resulting in the modified adsorbent consisting entirely of effectual adsorption composition. Compared with the unmodified adsorbent, the modified adsorbent exhibited higher adsorption capacity and uptake rate for carbon dioxide, because of the increase of effective adsorption surface and the decrease of diffusion resistance owing to conversion of kaolin binder into zeolite. The model parameters of isotherms and the isosteric heats calculated by the Clausius–Clapeyron equation for CO₂ adsorption showed the stronger interaction of adsorbate–adsorbent and the higher degree of heterogeneity of adsorption centers in modified than unmodified adsorbents.     

Adsorption of Cu(II) ions from aqueous solutions on biochars prepared from agricultural by-products

In this study, the adsorption of Cu(II) from aqueous solutions by agricultural by-products, such as rice husks, olive pomace and orange waste, as well as compost, was evaluated. The aim was to obtain sorbent materials (biochars) through hydrothermal treatment (300?°C) and pyrolysis (300?°C and 600?°C). The effect of adsorbent dose, pH, contact time and initial Cu(II) concentration in batch-mode experiments was investigated. The optimum Cu(II) adsorption conditions was found to occur at 5-12?g/L adsorbent dose, initial pH 5-6, and reaction time 2-4?h. Furthermore, the adsorption kinetics were best described by the pseudo-second order model for all the tested materials, while the adsorption equilibrium best fitted by the linear and Freundlich isotherms. Comparing rice husks and olive pomace, the higher adsorption capacity resulted after pyrolysis at 300?°C. With respect to the orange waste and compost, the highest adsorption capacity was observed using biochars obtained after hydrothermal treatment and pyrolysis at 300?°C.     

PATTERNS OF SUSPENDED SEDIMENT TRANSPORT IN A COASTAL ALASKA STREAM1

Suspended sediment data from a 154 ha watershed on northeast Chichagof Island, Alaska, were collected over three fall storm seasons from 1980 to 1982. Sediment rating curves for nine pooled storms explained less than 34 percent of the variation in total suspended solids (TSS). Significantly higher concentrations of suspended sediment occurred during the rising limb of storm hydrographs than for similar flows on the falling limb, accounting for hysteresis loops in TSS versus streamflow plots for individual storms. These hysteresis loops were wider during early season storms, indicating that easily transportable fine sediment may have been flushed from the upper portion of channel banks and from behind large organic debris during early season peak flows. Regression relationships (TSS versus Q) developed for the highest stormflows (> 1 m³/s) had steeper slopes than the lower stormflows (< 1 m³/s). Turbidity correlated well (r=0.94) with TSS for all storm-flow data combined. Organic matter constituted an average of 35 percent (by weight) of TSS for all water quality samples.     

TURBIDITY SUSPENI)ED SEDIMENT,AND WATER CLARITY: A REVIEW1

ABSTRACT: Suspended sediment causes a range of environmental damage, including benthic smothering, irritation of fish gills, and transport of sorbed contaminants. Much of the impact, while sediment remains suspended, is related to its light attenuation, which reduces visual range in water and light availability for photosynthesis. Thus measurement of the optical attributes of suspended matter in many instances is more relevant than measurement of its mass concentration. Nephelometric turbidity, an index of light scattering by suspended particles, has been widely used as a simple, cheap, instrumental surrogate for suspended sediment, that also relates more directly than mass concentration to optical effects of suspended matter. However, turbidity is only a relative measure of scattering (versus arbitrary standards) that has no intrinsic environmental relevance until calibrated to a ‘proper’ scientific quantity. Visual clarity (measured as Secchi or black disc visibility) is a preferred optical quantity with immediate environmental relevance to aesthetics, contact recreation, and fish habitat. Contrary to common perception, visual clarity measurement is not particularly subjective and is more precise than turbidity measurement. Black disc visibility is inter‐convertible with beam attenuation, a fundamental optical quantity that can be monitored continuously by beam transmissometry. Visual clarity or beam attenuation should supplant nephelometric turbidity in many water quality applications, including environmental standards.     

Using turbidity and acoustic backscatter intensity as surrogate measures of suspended sediment concentration in a small subtropical estuary

The suspended sediment concentration is a key element in stream monitoring, although the turbidity and acoustic Doppler backscattering may be suitable surrogate measures. Herein a series of new experiments were conducted in laboratory under controlled conditions using water and mud samples collected in a small subtropical estuary of Eastern Australia. The relationship between suspended sediment concentration and turbidity exhibited a linear relationship, while the relationships between suspended sediment concentration and acoustic backscatter intensity showed a monotonic increase. The calibration curves were affected by both sediment material characteristics and water quality properties, implying that the calibration of an acoustic Doppler system must be performed with the waters and soil materials of the natural system. The results were applied to some field studies in the estuary during which the acoustic Doppler velocimeter was sampled continuously at high frequency. The data yielded the instantaneous suspended sediment flux per unit area in the estuarine zone. They showed some significant fluctuations in instantaneous suspended mass flux, with a net upstream-suspended mass flux during flood tide and net downstream sediment flux during ebb tide. For each tidal cycle, the integration of the suspended sediment flux per unit area data with respect of time yielded some net upstream sediment flux in average.