Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.     

Evaluation of the multiple-ion competition in the adsorption of As(V) onto reclaimed iron-oxide coated sands by fractional factorial design

This study describes the competitive effects of selected ions and natural organic matter on As(V) removal using reclaimed iron-oxide coated sands (RIOCS) in the single- and multi-ion systems. A 2(7-3) factional factorial experimental design (FFD) was employed for screening main competitive factors in this adsorption process. As a result, the inhibitive competition effects of the anions on As(V) removal in the single ion system were in the following sequence: PO(4)(3-)>SiO(3)(2-)>HCO(3)(-)>humic acid (HA)>SO(4)(2-)>Cl(-), whereas the cation Ca(2+) was observed to enhance the As(V) removal. In addition, the optimum initial pH for As(V) removal in single-ion system was 5. Based on the estimates of major effects and interactions from the FFD, PO(4)(3-), SiO(3)(2-), Ca(2+) and HA were important factors on As(V) removal in the multi-ion system. The promoters for the As(V) removal were found to be Ca(2+) and, to a lesser extent, SO(4)(2-). The competitive effects of these ions on As(V) removal were in the order of PO(4)(3-), SiO(3)(2-), HA, HCO(3)(-), and Cl(-). In the single ion system, the efficiencies of As(V) removal range from 75% to 96%, much higher than those in the multi-ion system (44%) at the initial pH 5. Clearly, there were some complex anion interactions in the multi-ion system. To promote the removal of As(V) by RIOCS, it is proposed to lower the pH in the single-ion system, while in the multi-ion system, the increase of the Ca(2+) concentration, or decreases of PO(4)(3-), SiO(3)(2-) and HA concentrations is suggested.     

Adsorption of arsenic (V) on kaolinite and on kaolinite-humic acid complexes. Role of humic acid nitrogen groups

In order to investigate the influence of organic matter on arsenic retention, we used batch experiments at pH 7 to determine the adsorption of As(V) on three different solids: a crude, purified, Ca-exchanged kaolinite and two kaolinites coated with humic acids (HAs) having different nitrogen contents. We first examined the adsorption of each HA onto kaolinite, and then used the HA-kaolinite complexes to study As(V) adsorption. The results clearly show an influence of the HA coating on As adsorption. For example, with low initial As concentrations the solid/liquid partition coefficient (R(d)) for both HA complexes is greater than that for the crude kaolinite. We found that increasing the initial As concentrations decreased the R(d) values of the HA-coated kaolinites until finally they were the same as the crude kaolinite R(d) values. This suggests that adsorption occurs first on the HA sites and then, once the HA sites are saturated, on the remaining kaolinite sites. We also noted that the more reactive HA-kaolinite complex was the one with the highest N/C ratio. Comparing the amount of amine groups in the HA-kaolinite complexes with the total amount of adsorbed As indicates that the HA amine groups, due to their positive charge at pH 7, play a key role in the adsorption of As onto organic matter.     

Hydrological and environmental conditions as key drivers for spatial and seasonal changes in PCDD/PCDF concentrations, transport and deposition along urban cascade reservoirs

To investigate the drivers for transport and deposition of 17 2,3,7,8-substituted PCDDs/PCDFs along an urban river, water samples from five reservoirs located along the river course were collected in January and July 2008. The concentrations of 17 congeners of PCDD/PCDF were determined and compared to environmental - physical, chemical and biological - conditions. The obtained data revealed that the concentration of the sum of toxic PCDDs/PCDFs in water samples differ between reservoirs as well as between seasons, ranging from 12.04 pg L(-1) in UP (first in the cascade) to 1327.94 pg L(-1) in PR (last in the cascade) during winter of 2008; and from 34.94 pg L(-1) in UP to 1352.50 pg L(-1) in TR (next to last) in summer 2008. In comparison, water samples collected from the river had a concentration several times lower at the first two sites (sites no. 1 and 4) and no detectable values at the last three stations (sites no. 7, 8, 10). The obtained data demonstrated strong or moderate correlations between the sum of 17 PCDDs/PCDFs and TEQ in reservoir water samples and physical, chemical and biological conditions, such as: Mg(2+) (R=0.82; R=0.80, respectively), SO(4)(2-) (R=0.80; R=0.80, respectively), K(+) (R=0.80; R=0.80, respectively), Ca(2+) (R=0.67, R=0.70, respectively), OSM (R=0.63, R=0.70, respectively). In addition, the positive strong correlation between TEQ concentrations and the water temperature (R=0.63) and chlorophyll a content (R=0.90) was noted. The violent weather conditions occurred during the research season with periods of intensive storm events (up to 32 mm in mid July), and thus the increased river flow velocity (up to 0.45 m(3)s(-1)) could have a direct and indirect influence on PCDDs/PCDFs concentration through changes in the sedimentation/resuspension ratio and consequently in transport, deposition and degradation processes along the river/reservoirs.     

Throughfall chemistry and canopy interactions in a Sitka spruce plantation sprayed with six different simulated polluted mist treatments

Throughfall chemistry was studied in a mature Sitka spruce plantation in order to investigate canopy interactions, such as nitrogen absorption, cation leaching, and neutralization of rainfall passing through the canopy. The plantation had been exposed to six different simulated mist treatments including N (NH(4)NO(3)) and S (H(2)SO(4) at pH 2.5) in four replicated blocks since 1996. Throughfall and rainfall were collected from May to September 2000. The results showed that 30-35% of the applied N was retained by the canopy. There were linear relationships between the loss of H(+) and increased K(+), Mg(2+) and Ca(2+) deposition through the canopy. However these increases in K(+), Mg(2+) and Ca(2+) deposition accounted for only about 50% of total neutralization of the acidity. The relationship between the anion deficits in throughfall and the loss of H(+) implied that weak organic acid anions were involved in the neutralization of the acidity in throughfall.     

Optimum conditions for microbial carbonate precipitation

The type of bacteria, bacterial cell concentration, initial urea concentration, reaction temperature, the initial Ca(2+) concentration, ionic strength, and the pH of the media are some factors that control the activity of the urease enzyme, and may have a significant impact on microbial carbonate precipitation (MCP). Factorial experiments were designed based on these factors to determine the optimum conditions that take into consideration economic advantage while at the same time giving quality results. Sporosarcina pasteurii strain ATCC 11859 was used at constant temperature (25°C) and ionic strength with varying amounts of urea, Ca(2+), and bacterial cell concentration. The results indicate that the rate of ureolysis (k(urea)) increases with bacterial cell concentration, and the bacterial cell concentration had a greater influence on k(urea) than initial urea concentration. At 25 mM Ca(2+) concentration, increasing bacterial cell concentration from 10(6) to 10(8)cells mL?1 increased the CaCO(3) precipitated and CO(2) sequestrated by over 30%. However, when the Ca(2+) concentration was increased 10-fold to 250 mM Ca(2+), the amount of CaCO(3) precipitated and CO(2) sequestrated increased by over 100% irrespective of initial urea concentration. Consequently, the optimum conditions for MCP under our experimental conditions were 666 mM urea and 250 mM Ca(2+) at 2.3×10? cells mL?1 bacterial cell concentration. However, a greater CaCO(3) deposition is achievable with higher concentrations of urea, Ca(2+), and bacterial cells so long as the respective quantities are within their economic advantage. X-ray Diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray analyzes confirmed that the precipitate formed was CaCO(3) and composed of predominantly calcite crystals with little vaterite crystals.     

Ca(2+) -dependent plant response to Pb(2+) is regulated by LCT1

Tobacco plants transformed with TaLCT1 were cultured on Knop's medium with modified calcium concentrations (0.01-3 mM) in the presence of Pb(2+), and in soil contaminated by lead. A 4-5 microM Pb(2+) administered in the presence of 1 mM Ca(2+) inhibited the root growth of transgenic plants to much lesser degree than of control plants, whereas in the presence of 3mM Ca(2+) no differences were found between the studied lines. The reduction of Pb(2+) toxicity in the presence of 1 mM Ca(2+) was not accompanied by a change in the lead tissue concentration. However, when Ca(2+) level in the medium was lowered to 0.01 mM, several fold higher root/shoot Pb ratio in transgenic plants was observed, twofold increase in the total amount of metal accumulated, and lower concentration of Pb in the xylem sap. Results suggest the involvement of TaLCT1 in the regulation of Ca-dependent Pb-detoxification, and under conditions of low calcium in lead uptake and distribution.     

Effects of pH, organic acids, and inorganic ions on lead desorption from soils

The desorption characteristics of lead in two variable charge soils (one developed from Arenaceous rock (RAR) and the other derived from Quaternary red earths (REQ)) were studied, and the effects of pH value, organic acid, and competitive ions were examined. Desorption of Pb(2+) decreased from nearly 100.0 to 20.0% within pH 1.0-4.0 in both soils, and then the decrease diminished at pH > 4.0. Organic ligands at relatively low concentrations (< or =10(-3) mol L(-1)) slightly inhibited Pb(2+) desorption, but enhanced Pb(2+) desorption at higher concentrations. In this study, citric acid or acetic acid at higher concentrations (>10(-3) mol L(-1)) had the greatest improvement of Pb(2+) desorption, followed by malic acid; and the smallest was oxalic acid. Desorption of the adsorbed Pb(2+) increased greatly with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Pb(2+) desorption more than Zn(2+) at the same loading.     

Desorption of arsenic from clay and humic acid-coated clay by dissolved phosphate and silicate

Arsenic (As) contaminated aquifers contain iron minerals and clays that strongly bind As at their surfaces. It was suggested that As mobilization is driven by natural organic matter (including fulvic acids (FA) and humic acids (HA)) present in the aquifers either via providing reducing equivalents for reductive dissolution of Fe(III) (hydr)oxides or via competitive desorption of As from the mineral surfaces. In the present study we quantified sorption of As(III) and As(V) to Ca(2+)-homoionized illite (IL) and to kaolinite (Kao) as well as to HA-coated clays, i.e., illite-HA (IL-HA) and kaolinite-HA (Kao-HA) at neutral pH. Clay-HA complexes sorbed 28-50% more As than clay-only systems upon addition of 100μM As(III)/As(V) to 0.5g of clay or HA-clay with Ca(2+) probably playing an important role for HA binding to the clay surface and As binding to the HA. When comparing sorption of As(V) and As(III) to clay and HA-clay complexes, As(V) sorption was generally higher by 15-32% than sorption of As(III) to the same complexes. IL and IL-HA sorbed 11-28% and 6-11% more As compared to Kao and Kao-HA, respectively. In a second step, we then followed desorption of As from Kao, Kao-HA, IL and IL-HA by 100 and 500μM phosphate or silicate both at high (0.41-0.77μmol As/g clay), and low (0.04 to 0.05μmol As/g clay) As loadings. Phosphate desorbed As to a larger extent than silicate regardless of the amount of As loaded to clay minerals, both in the presence and absence of HA, and both for illite and kaolinite. At high loadings of As, the desorption of both redox species of As from clay-HA complexes by phosphate/silicate ranged from 32 to 72% compared to 2-54% in clay only systems meaning that As was desorbed to a larger extent from HA-coated clays compared to clay only systems. When comparing As(III) desorption by phosphate/silicate to As(V) desorption in high As-loading systems, there was no clear trend for which As species is desorbed to a higher extent in the four clay systems meaning that both As species behave similarly regarding desorption from clay surfaces by phosphate/silicate. Similarly, no significant differences were found in high As-loading systems in the amount of As desorbed by phosphate/silicate when comparing Kao vs. IL and Kao-HA vs IL-HA systems meaning that both clay types behave similarly regarding desorption of As by phosphate/silicate. At low As loadings, up to 80% of As was desorbed by phosphate and silicate with no noticeable differences being observed between different As species, different types of clay, clay vs clay-HA or the type of desorbant (phosphate and silicate). The results of this study showed that HA sorption to Ca(2+)-homoionized clay minerals can increase As binding to the clay although the As sorbed to the clay-HA is also released to a greater extent by competing ions such as phosphate and silicate. Desorption of As depended on the initial loadings of As onto the clay/clay-HA. Based on our results, the effect of humic substances on sorption of As and on desorption of As by phosphate and silicate has to be considered in order to fully understand and evaluate the environmental behavior of As in natural environments.     

Stemflow chemistry of urban street trees

pH and ion concentrations (Na(+), K(+), Mg(2+), Ca(2+), NO(-)(3)) in the stemflow of the evergreen broad-leaved tree, Ilex rotunda, planted in the median strip of a highway and nitrogen oxides concentration in the air in an urban site were compared with a suburban site in Fukuoka city, Japan. The annual average of the nitrogen oxides concentration in the air was higher and NO(-)(3) concentration in the stemflow at the urban site was higher or similar compared with the suburban site. However, the annual average of pH in the stemflow at the urban site was higher than at the suburban. The annual average cation concentrations in the stemflow at the urban site were higher than at the suburban except Na(+). In particular, K(+) and Ca(2+) were higher throughout the measurement period. Therefore, higher pH in the urban stemflow was probably due to neutralization by higher concentrations of K(+), Mg(2+) and Ca(2+).     

Evaluation of solubilizing ability of humic aggregate basing on the phase-separation model

Solubilizing abilities of aggregates of humic acid (HA) to chlorinated benzenes (CBs) were investigated by means of the apparent water solubility enhancement. Both the water solubilities of 1,4-dichlorobenzene (DCB) and 1,2,4,5-tetrachlorobenzene (TeCB) linearly increased with increasing concentration of HA above the critical micelle concentration (CMC). Such solubilization behavior of CBs for HA was compatible with those for sodium dodecyl sulfate (SDS). These results indicate that the solubilization of CBs in the aqueous solution of HA above the CMC can be interpreted on the basis of the phase-separation model. Thus, the partition coefficients (K(mic)) of CBs between water and HA aggregate phases were calculated by assuming this model. The fact that the K(mic) value increased with increasing K(ow) of CBs supported the partition into the HA aggregate phase by hydrophobic interaction. The estimated K(mic) values of DCB were not dependent on the solution pH. Both K(mic) values of DCB and TeCB for the HA aggregate were found to be 4-5-fold lower than those of SDS.     

In vitro and in vivo studies of lead immobilization by synthetic hydroxyapatite

Apatite appears a useful compound for removing lead from water, due to its ability to immobilize the metal by precipitation. In dilute solution, dissolved hydroxyapatite [HA, Ca1O(P04)6(OH)2] provided phosphates that were reactive with aqueous lead (molar ratio HA/Pb= 1/10) forming precipitates at around pH 6. These dissolved at a more acidic pH (3). Solid HA in contact with Pb2+ions, led to the formation of pyromorphite [Pblo(P04)6(OH)2], identified by X-ray diffraction and insoluble at pH tested (3-8). The amount of pyromorphite increased with the weight ratio of HA/Pb. When this one increased from 1 to 1000, lead precipitated as pyromorphite rose from 19 to 99%. In vivo experiments on rats confirmed the in vitro results. In fact, lead bioavailability assessed by intestinal perfusion was unchanged in the presence of dissolved HA, whereas it was significantly lower in the presence of solid HA, evaluated by gastric intubation, at a weight ratio equal to 10 (amount of lead absorbed decreased by 60%). Apatite could bean effective means of immobilizing lead in drinking or sewage, since accidental pyromorphite ingestion does not yield bioavailable lead.     

Regional variation in the chemical composition of winter snow pack and terricolous lichens in relation to sources of acid emissions in the Usa river basin,northeast European Russia

The chemical composition of snow and terricolous lichens was determined along transects through the Subarctic towns of Vorkuta (130 km west-east), Inta (240 km south-north) and Usinsk (140 km, southwest-northeast) in the Usa river basin, northeast European Russia. Evidence of pollution gradients was found on two spatial scales. First, on the Inta transect, northward decreases in concentrations of N in the lichen Cladonia stellaris (from 0.57 mmol N g(-1) at 90 km south to 0.43 mmol N g(-1) at 130 km north of Inta) and winter deposition of non-sea salt sulphate (from 29.3 to 12.8 mol ha(-1) at 90 km south and 110 km north of Inta, respectively) were attributed to long range transport of N and S from lower latitudes. Second, increased ionic content (SO42-, Ca2+, K+) and pH of snow, and modified N concentration and the concentration ratios K+:Mg2+ and K+: (Mg2++Ca2+) in lichens (Cladonia arbuscula and Flavocetraria cucullata) within ca. 25-40 km of Vorkuta and Inta were largely attributed to local deposition of alkaline coal ash. Total sulphate concentrations in snow varied from ca. 5 micromol l(-1) at remote sites to ca. 19 micromol l(-1) near Vorkuta. Nitrate concentration in snow (typically ca. 9 micromol l(-1)) did not vary with proximity to perceived pollution sources.     

Laboratory investigation of flux reduction from dense non-aqueous phase liquid (DNAPL) partial source zone remediation by enhanced dissolution

This study investigated the benefits of partial removal of dense nonaqueous phase liquid (DNAPL) source zones using enhanced dissolution in eight laboratory scale experiments. The benefits were assessed by characterizing the relationship between reductions in DNAPL mass and the corresponding reduction in contaminant mass flux. Four flushing agents were evaluated in eight controlled laboratory experiments to examine the effects of displacement fluid property contrasts and associated override and underride on contaminant flux reduction (R(j)) vs. mass reduction (R(m)) relationships (R(j)(R(m))): 1) 50% ethanol/50% water (less dense than water), 2) 40% ethyl-lactate/60% water (more dense than water), 3) 18% ethanol/26% ethyl-lactate/56% water (neutrally buoyant), and 4) 2% Tween-80 surfactant (also neutrally buoyant). For each DNAPL architecture evaluated, replicate experiments were conducted where source zone dissolution was conducted with a single flushing event to remove most of the DNAPL from the system, and with multiple shorter-duration floods to determine the path of the R(j)(R(m)) relationship. All of the single-flushing experiments exhibited similar R(j)(R(m)) relationships indicating that override and underride effects associated with cosolvents did not significantly affect the remediation performance of the agents. The R(j)(R(m)) relationship of the multiple injection experiments for the cosolvents with a density contrast with water tended to be less desirable in the sense that there was less R(j) for a given R(m). UTCHEM simulations supported the observations from the laboratory experiments and demonstrated the capability of this model to predict R(j)(R(m)) relationships for non-uniformly distributed NAPL sources.     

Influences of metals on kinetics of methyl tert-butyl ether biodegradation by Ochrobactrum cytisi

The influence of zinc, manganese, and nickel on the degradation of MTBE (methyl tert-butyl ether), by an aerobic MTBE-degrading strain, Ochrobactrum cytisi, were investigated. The result showed that unlike previous findings, O. cytisi was able to degrade MTBE through direct metabolism when MTBE was present as the only carbon source. The degradation rate of MTBE was rapid, completed within 80 h. MTBE biodegradation by this strain was stimulated at low concentrations of Zn(2+) (1-5 mg l(-1)) and Mn(2+) (1-5 mg l(-1)) but inhibited at high concentrations of Zn(2+) (20 mg l(-1)) and Mn(2+) (20 mg l(-1)), and at low concentration of Ni(2+) (1-4 mg l(-1)). Kinetic parameters for MTBE degradation in the presence or absence of metals were obtained through nonlinear regression and a least-square minimization procedure. In all cases, a good agreement was achieved between kinetic simulations and experimental results.     

Simulation modeling for nitrogen removal and experimental estimation of mass fractions of microbial groups in single-sludge system

Nitrification-denitrification in a single-sludge nitrogen removal system (SSNRS; with a sufficient carbon source for denitrification) was performed. With an increase in the mixed liquor recycle ratio (R(m)) from 1 to 2, the total nitrogen (TN) removal efficiency at a lower volumetric loading rate (VLR=0.21 NH(4)(+)-N m(-3) d(-1)) increased, but the TN removal efficiency at a higher VLR (0.35 kg NH(4)(+)-N m(-3) d(-1)) decreased. A kinetic model that accounts for the mass fractions of Nitrosomonas, Nitrobacter, nitrate reducer and nitrite reducer (f(n1), f(n2), f(dn1), and f(dn2)) in the SSNRS and an experimental approach for the estimation of the mass fractions of nitrogen-related microbial groups are also proposed. The estimated f(dn1) plus f(dn2) (0.65-0.83) was significantly larger than the f(n1) plus f(n2) (0.28-0.32); the f(n1) (0.21-0.26) was larger than the f(n2) (0.05-0.07); and the f(dn1) (0.32-0.45) varied slightly with the f(dn2) (0.33-0.38). At the lower VLR, the f(dn1) plus f(dn2) increased with increasing R(m); however at the higher VLR, the f(dn1) plus f(dn2) did not increase with increasing R(m). By using the kinetic model, the calculated residual NH(4)(+)-N and NO(2)(-)-N in the anoxic reactor and NO(2)(-)-N and NO(3)(-)-N in the aerobic reactor were in fairly good agreement with the experimental data; the calculated NO(3)(-)-N in the anoxic reactor was over-estimated and the calculated NH(4)(+)-N in the aerobic reactor was under-estimated.     

Sorption of sodium dodecylbenzene sulfonate by montmorillonite

Sorption of linear alkylbenzene sulfonates by soils and sediments is an important process that may affect their fate, transport, toxicity and their application in remediation of contaminated soil and groundwater. In this study, batch experiments were conducted to elucidate the sorption of a widely used anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), by montmorillonite. It was observed that: (i) SDBS was sorbed significantly by montmorillonite saturated with Ca(2+), but little by Na-saturated montmorillonite; (ii) the amount of SDBS sorbed by Ca(2+)-montmorillonite was enhanced by NaCl; and (iii) no significant intercalation of SDBS into Ca(2+)-montmorillonite was observed by X-ray diffraction (XRD) analysis. These results indicate that the removal of SDBS by Ca(2+)-montmorillonite was primarily attributed to the precipitation between DBS(-) and Ca(2+) in solution which was released from montmorillonite via cation exchange. These results will help us to understand the sorption behavior and environmental effects of anionic surfactants.     

Photoinductive activity of humic acid fractions with the presence of Fe(III): the role of aromaticity and oxygen groups involved in fractions

Relationship between the photoinductive activity and the properties of humic acids (HA) fractions were investigated with and without Fe(III). Three fractions were separated based on the molecular weight (M(w)) and were obtained following the order of M(w): F(A)>F(B)>F(C). Compared to F(A) and F(B), photodegradation of atrazine under simulated sunlight was much faster in solution containing F(C), whose structure was dominated by greater aromaticity, more oxygen groups and fluorophores. The interaction of HA fractions and Fe(III) was studied using fluorescence spectrometry and F(C) had the largest quenching constant. The capacity of electron transfer, estimated from the amount of photoformed Fe(II), was also highest for F(C). Thus, the Fe(III)-F(C) complex was efficient in phototransformation of atrazine in nearly neutral aqueous solutions. These results suggest that the aromaticity and oxygen groups content of HA exert great influence on the binding ability of metals and on the fate of pollutants in natural waters.     

Direct and indirect photolysis of cyhalofop in aqueous systems

The photodegradation of the aryloxyphenoxy propionic herbicide cyhalofop-butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), and of its primary metabolite (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA) was studied in water at different irradiation wavelengths. The sunlight irradiation was investigated also in the presence of humic acid (HA), Fe oxide, titanium dioxide (TiO₂) and zinc oxide (ZnO) as photocatalysts.CyB and CyA were rapidly degraded by UV irradiation. CyB afforded the butyl ester of 2-[3-(4-cyano-2-fluorophenyl)-4-hydroxy-phenoxy]propanoic acid (CyI), a metabolite arising from a photo-Fries rearrangement. Instead, CyA yielded (R)-2-4-(4-carboxyl-2-fluorophenoxy)phenoxypropanoic acid (CyD), a dicarboxylic acid arising from the photo-hydrolysis of cyano group via amide. CyB was stable in simulated sunlight also in the presence of the catalysts tested.The irradiation of a CyA solution, in the presence of HA or Fe oxide, with simulated sunlight did not produce any significant degradation. In the same experimental conditions, CyA was totally mineralized in the presence of TiO₂ and ZnO.     

Atmospheric input of elements to forest ecosystems: a method of estimation using artificial foliage placed above rain collectors

Usefulness of a method of artificial foliage was tested for estimation of total ionic inputs from the atmosphere to forest ecosystems, as well as of processes relevant to ionic fluxes through tree canopies: uptake, leaching, passive flow. The studies were performed in Norway spruce and European beech stands in Karkonosze Mountains (Poland), in 1995-97. Artificial leaves of increasing leaf area index: 0, 2, 6 and 12 m(2) m(-2 )were placed above standard rain collectors. It has been found that total atmospheric fluxes of H(+), NH(4)(+), Ca(2+), Mg(2+), Pb(2+), NO(3)(-) and SO(4)(2-) rose as surface area of the foliage increased. This was especially true for nitrate, sulphate and ammonium. No such relationship was found for K(+), Na(+), Zn(2+), Cd(2+), Cu(2+) and PO(4)(3-). The increase in anion fluxes exceeded that in neutralising cations (NH(4)(+), Na(+), K(+), Mg(2+), Ca(2+)) and led to progressive rainwater acidification with the increase in the foliage area. An analysis of net canopy exchange (atmospheric input-throughfall flux) has shown that SO(4)(2-), PO(4)(3-), Na(+), Ca(2+) and Cu(2+) flowed passively through the tree crowns; NH(4)(+), NO(3)(-), Zn(2+), Cd(2+) and occasionally Pb(2+) were efficiently absorbed, whereas K(+) was leached from the canopies. Beech was more effective in modifying ionic pool from the atmosphere than spruce. This related to H(+) (greater absorption) and Mg(2+) (greater leaching). It has been demonstrated that the results concerning trends in net canopy exchange and produced by the simple method of artificial foliage are comparable to more sophisticated techniques of the measurements. This proves the method to be useful.