Dissipation and metabolism of C-spiroxamine in soil under laboratory condition

Spiroxamine [SPX] belongs to a spiroketalamine group of substances. The biodegradation of [1,3-dioxolane-4-¹⁴C]-SPX has been examined in 2 soils of different physicochemical properties. The total recovery of radioactivity from soils was 98.6-103.5% of that applied. The total amount of extractable radioactivity declined with a simultaneous increase in non-extractable radioactivity. Volatile organics were detected at lower levels; however, mineralization played a marked effect on the route of SPX dissipation. The half-life ranges between 37 and 44 d. SPX does not undergo any enantioselective degradation. 4 metabolites: despropyl-SPX, desethyl-SPX, SPX N-oxide and SPX acid were identified, applying mass spectrometric technique. Sorption-desorption data fitted well with a Freundlich model in log form (r², 0.99). K_Dsorp ranged between 44 and 230, suggesting SPX ought to be considered as a substance with low leaching potential [groundwater ubiquity score (GUS), <1.8]. Furthermore, an overall low desorption of 1-11% indicates firm retention of SPX by the soils.     

An oxygenated metabolite of benzo[a]pyrene increases hepatic β-oxidation of fatty acids in chick embryos

Polycyclic aromatic hydrocarbons (PAHs) are well-known carcinogens to humans and ecotoxicological effects have been shown in several studies. However, PAHs can also be oxidized into more water soluble-oxygenated metabolites (Oxy-PAHs). The first purpose of the present project was to (1) assess the effects of a mixture containing three parent PAHs: anthracene, benz[a]anthracene, and benzo[a]pyrene versus a mixture of their oxygenated metabolites, namely: anthracene-9,10-dione, benz[a]anthracene-7,12-dione, and 9,10-dihydrobenzo[a]pyrene-7-(8H)-one on the hepatic fatty acid β-oxidation in chicken embryos (Gallus gallus domesticus) exposed in ovo. The second and also main purpose of the project was to (2) assess the effects of the parent PAHs versus their oxy-PAHs analogues when injected individually, followed by (3) additional testing of the individual oxy-PAHs. The hepatic β-oxidation was measured using a tritium release assay with [9,10-³H]-palmitic acid (16:0) as substrate. The result from the first part (1) showed reduced hepatic β-oxidation after exposure in ovo to a mixture of three PAHs, however, increased after exposure to the mixture of three oxy-PAHs compared to control. The result from the second part (2) and also the follow-up experiment (3) showed that 9,10-dihydrobenzo[a]pyrene-7-(8H)-one was the causative oxy-PAH. The implication of this finding on the risk assessment of PAH metabolite exposure in avian wildlife remains to be determined. To the best of our knowledge, no similar studies have been reported.     

Anaerobic testosterone degradation in Steroidobacter denitrificans - Identification of transformation products

The transformation of the androgenic steroid testosterone by gammaproteobacterium Steroidobacter denitrificans was studied under denitrifying conditions. For the first time, growth experiments showed that testosterone was mineralized under consumption of nitrate and concurrent biomass production. Experiments with cell suspensions using [4-¹⁴C]-testosterone revealed the intermediate production of several transformation products (TPs). Characterisation of ten TPs was carried out by means of HPLC coupled to high resolution mass spectrometry with atmospheric pressure chemical ionization as well as ¹H and ¹³C NMR spectroscopy. 3β-hydroxy-5α-androstan-17-one (trans-androsterone) was formed in the highest amount followed by 5α-androstan-3,17-dione. The data suggests that several dehydrogenation and hydrogenation processes take place concurrently in ring A and D because no consistent time-resolved pattern of TP peaks was observed and assays using 2 TPs as substrates resulted in essentially the same TPs. The further transformation of testosterone in S. denitrificans seems to be very efficient and fast without formation of detectable intermediates.     

Toxicity of various anions associated with methoxyethyl methyl imidazolium-based ionic liquids on Clostridium sp

We investigated the effects on the growth of the anaerobic bacterium, Clostridium sp., of the ionic liquid, 1-methoxyethyl-3-methyl imidazolium [MOEMIM]⁺, derived from imidazolium cation and paired with one of a variety of counter-ions, viz., tetrafluoroborate [BF₄]^-, hexafluorophosphate [PF₆]^-_, trifluoroacetate [CF₃COO]^-, bis(trifluoromethane)sulfonamide [Tf₂N]^-, methane sulfonate [OMS], and 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF₄]. These anions, in association with [MOEMIM]⁺ lowered the growth rate of the bacterium, showing the following trend: [Tf₂N]^- ≧ [PF₆]^- > [BF₄]^- > [CF₃COO]^- > [OMS]⁻. Anions incorporating fluorine were more toxic than those without it, and their toxicity rose with an increase in the number of fluorine atoms. Also, [MOEMIM]⁺[BF₄]^- was less toxic than [BMIM]⁺[BF₄]^-, probably due to the presence of a methoxyethyl functional group integrated in the cation side chain.     

Role of some organic inhibitors on the oxidation of dissolved sulfur dioxide by oxygen in rainwater medium

In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R _o = k _o[S(IV)]], where k _o is the first-order rate constant and R _o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k _obs = k _o/(1 + B [Inh]), where k _obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10^?5 to 1.5?×?10^?4 s^?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?10⁴) (ethanol) and (3.95?±?2.36)?×?10⁴ (2-butanol) at 25 °C.     

Phthalate and PAH concentrations in dust collected from Danish homes and daycare centers

As part of the Danish Indoor Environment and Children’s Health (IECH) study, dust samples were collected from 500 bedrooms and 151 daycare centers of children (ages 3 to 5) living on the island of Fyn. The present paper reports results from the analyses of these samples for five phthalate esters (diethyl phthalate (DEP), di(n-butyl) phthalate (DnBP), di(isobutyl) phthalate (DiBP), butyl benzyl phthalate (BBzP), di(2-ethylhexyl) phthalate (DEHP)) and three PAHs (pyrene, benz[a]anthracene (B[a]A) and benzo[a]pyrene (B[a]P)). The three PAHs and DEHP were detected in dust samples from all sites, while DEP, DnBP, DiBP and BBzP were detected in more than 75% of the bedrooms and more than 90% of the daycare centers. The dust mass-fractions of both phthalates and PAHs were log-normally distributed. With the exception of DEP, the mass-fractions of phthalates in dust were higher in daycare centers than homes; PAH mass-fractions in dust were similar in the two locations. There was no correlation among the different phthalates in either homes or daycare centers. In contrast, the PAH were correlated with one another – more strongly so in homes (R² = 0.80–0.90) than in daycare centers (R² = 0.28–0.45). The dust levels of several phthalates (BBzP, DnBP and DEHP) were substantially lower than those measured in a comparable study conducted 6–7 years earlier in Sweden. Although usage patterns in Denmark differ from those in Sweden, the current results may also reflect a change in the plasticizers that are used in common products including toys. PAH levels were roughly an order of magnitude lower than those measured in Berlin and Cape Cod residences, suggesting that the Danish sites are less impacted by motor vehicle emissions.     

Can Hediste diversicolor (Nereidae, Polychaete) be considered a good candidate in evaluating PAH contamination? A multimarker approach

The aim of this study was to develop a preliminary characterization of the biological responses of Hediste diversicolor to polycyclic aromatic hydrocarbons (PAHs) under controlled laboratory conditions. In order to test the effects of PAH exposure, a battery of biomarkers was applied to the polychaetes by exposing them to sublethal concentrations of benzo[a]pyrene (0.1 and 0.5 mg L⁻¹) for 10 d under laboratory conditions. The battery of biomarkers tested included oxidative stress biomarkers (glutathione content, enzymatic activities of catalase, glutathione S-transferases, glutathione reductase, glutathione peroxidases), total oxyradical scavenging capacity (TOSC) toward peroxyl and hydroxyl radicals and activity of acyl CoA oxidase (AOX) as a marker of peroxisome proliferation measured in the entire body; lipofuscin and neutral lipid accumulations and levels of Ca²⁺-ATPase activity analyzed in the intestinal epithelium; lysosomal membrane stability and genotoxic effects measured as DNA strand breaks and frequency of micronuclei in coelomocytes. Chemical analyses were also carried out to verify the polychaete’s benzo[a]pyrene (B[a]P) bioaccumulation levels after the exposure period. The results obtained indicate that B[a]P caused significant changes in most of the parameters measured in H. diversicolor. Biological responses to the organic compound were particularly significant for the biomarkers measured in the intestinal epithelium and in coelomocytes, emphasizing that these tissues were more affected during our experimental conditions. Considering the key trophic role of this benthic species in estuarine and coastal ecosystems, this study confirmed that H. diversicolor is an appropriate bioindicator of organic contamination.     

Phytoremediation for co-contaminated soils of chromium and benzo[a]pyrene using Zea mays L.

A greenhouse experiment was carried out to investigate the single effect of benzo[a]pyrene (B[a]P) or chromium (Cr) and the joint effect of Cr–B[a]P on the growth of Zea mays, its uptake and accumulation of Cr, and the dissipation of B[a]P over 60 days. Results showed that single or joint contamination of Cr and B[a]P did not affect the plant growth relative to control treatments. However, the occurrence of B[a]P had an enhancing effect on the accumulation and translocation of Cr. The accumulation of Cr in shoot of plant significantly increased by?≥?79 % in 50 mg kg^?1 Cr–B[a]P (1, 5, and 10 mg kg^?1) treatments and by?≥?86 % in 100 mg kg^?1 Cr–B[a]P (1, 5, and 10 mg kg^?1) treatments relative to control treatments. The presence of plants did not enhance the dissipation of B[a]P in lower (1and 5 mg kg^?1) B[a]P contaminated soils; however, over 60 days of planting Z. mays seemed to enhance the dissipation of B[a]P by over 60 % in 10 mg kg^?1 single contaminated soil and by 28 to 41 % in 10 mg kg^?1B[a]P co-contaminated soil. This suggests that Z. mays might be a useful plant for the remediation of Cr–B[a]P co-contaminated soil.     

Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

BVOC emissions, photosynthetic characteristics and changes in chloroplast ultrastructure of Platanus orientalis L. exposed to elevated CO2 and high temperature

To investigate the interactive effects of increasing [CO₂] and heat wave occurrence on isoprene (IE) and methanol (ME) emissions, Platanus orientalis was grown for one month in ambient (380 μmol mol⁻¹) or elevated (800 μmol mol⁻¹) [CO₂] and exposed to high temperature (HT) (38 °C/4 h). In pre-existing leaves, IE emissions were always higher but ME emissions lower as compared to newly-emerged leaves. They were both stimulated by HT. Elevated [CO₂] significantly reduced IE in both leaf types, whereas it increased ME in newly-emerged leaves only. In newly-emerged leaves, elevated [CO₂] decreased photosynthesis and altered the chloroplast ultrastructure and membrane integrity. These harmful effects were amplified by HT. HT did not cause any unfavorable effects in pre-existing leaves, which were characterized by inherently higher IE rates. We conclude that: (1) these results further prove the isoprene's putative thermo-protective role of membranes; (2) HT may likely outweigh the inhibitory effects of elevated [CO₂] on IE in the future.     

Removal of heavy metal ions from wastewater by a novel HEA/AMPS copolymer hydrogel: preparation, characterization, and mechanism

This study aims to synthesize 2-hydroxyethyl acrylate (HEA) and 2-acrylamido-2-methylpropane sulfonic (AMPS) acid-based hydrogels by gamma radiation and to investigate their swelling behavior and heavy metal ion adsorption capabilities. The copolymer hydrogels prepared were characterized via scanning electron microscopy, Fourier transformed infrared spectra, thermal gravimetric analysis, and X-ray photoelectron spectroscopy. The research showed that the copolymer hydrogel was beneficial for permeation due to its porous structure. In addition, the experimental group A-2-d [70 % water volume ratio and (n (AMPS)/n (HEA))?=?1:1] was an optimal adsorbent. The optimal pH was 6.0 and the optimal temperature was 15 °C. Pb²⁺, Cd²⁺, Cu²⁺, and Fe³+ achieved adsorption equilibriums within 24 h, whereas Cr³⁺ reached equilibrium in 5 h. Pb²+, Cd²⁺, Cr³⁺, and Fe³⁺ maximum load capacity was 1,000 mg L^?1, whereas the Cu²⁺ maximum capacity was 500 mg L^?1. The priority order in the multicomponent adsorption was Cr³⁺>Fe³⁺>Cu²⁺>Cd²⁺>Pb²⁺. The adsorption process of the HEA/AMPS copolymer hydrogel for the heavy metal ions was mainly due to chemisorption, and was only partly due to physisorption, according to the pseudo-second-order equation and Langmuir adsorption isotherm analyses. The HEA/AMPS copolymer hydrogel was confirmed to be an effective adsorbent for heavy metal ion adsorption.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Predicting bioavailability of PAHs in field-contaminated soils by passive sampling with triolein embedded cellulose acetate membranes

Triolein embedded cellulose acetate membrane (TECAM) was used for passive sampling of the fraction of naphthalene, phenanthrene, pyrene and benzo[a]pyrene in 18 field-contaminated soils. The sampling process of PAHs by TECAM fitted well with a first-order kinetics model and PAHs reached 95% of equilibrium in TECAM within 20 h. Concentrations of PAHs in TECAM (C_TECAM) correlated well with the concentrations in soils (r² = 0.693-0.962, p < 0.001). Furthermore, concentrations of PAHs determined in the soil solution were very close to the values estimated by C_TECAM and the partition coefficient between TECAM and water (K_TECAM-w). After lipid normalization nearly 1:1 relationships were observed between PAH concentrations in TECAMs and earthworms exposed to the soils (r² = 0.591-0.824, n = 18, p < 0.01). These results suggest that TECAM can be a useful tool to predict bioavailability of PAHs in field-contaminated soils.     

Investigation of low-level <Superscript>242</Superscript>Pu contamination on nutrition disturbance and oxidative stress in <Emphasis Type="Italic">Solanum tuberosum</Emphasis> L.

Plutonium associated with higher molecular weight molecules is presumed to be poorly mobile and hardly plant available. In our present study, we investigate the uptake and effects of Pu treatments on Solanum tuberosum plants in amended Hoagland medium at concentrations of [²⁴²Pu] = 100 and 500 nm, respectively. We found a direct proof of oxidative stress in the plants caused by these rather low concentrations. For the confirmation of oxidative stress, we explored the production of nitric oxide (NO) and hydrogen peroxide (H₂O₂) by epifluorescence microscopy. Oxidative stress markers like lipid peroxidation and superoxide radicals (O₂ ^??) are monitored through histochemical analysis. The biochemical parameters i.e. chlorophyll and carotenoids are measured as an indicator of cellular damage in the tested plants including the enzymatic parameters such as catalase and glutathione reductase. From our work, we conclude that Pu in low concentration has no significant effects on the uptake of many trace and macroelements. In contrast, the content of O₂ ^?? , malondialdehyde (MDA), and H₂O₂ increases with increasing Pu concentration in the solution, while the opposite effects was found for NO, catalase, and glutathione reductase. These findings prove that even low concentration of Pu regulates ROS production and generate oxidative stress in S. tuberosum L.     

Hydrolysis of di-n-butyl phthalate, butylbenzyl phthalate and di(2-ethylhexyl) phthalate in human liver microsomes

Diester phthalates are industrial chemicals used primarily as plasticizers to import flexibility to polyvinylchloride plastics. In this study, we examined the hydrolysis of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP) in human liver microsomes. These diester phthalates were hydrolyzed to monoester phthalates (mono-n-butyl phthalate (MBP) from DBP, mono-n-butyl phthalate (MBP) and monobenzyl phthalate (MBzP) from BBzP, and mono(2-ethylhexyl) phthalate (MEHP)) by human liver microsomes. DBP, BBzP and DEHP hydrolysis showed sigmoidal kinetics in V-[S] plots, and the Hill coefficient (n) ranged 1.37-1.96. The S₅₀, V_max and CL_max values for DBP hydrolysis to MBP were 99.7 μM, 17.2 nmol min⁻¹ mg⁻¹ protein and 85.6 μL min⁻¹ mg⁻¹ protein, respectively. In BBzP hydrolysis, the values of S₅₀ (71.7 μM), V_max (13.0 nmol min⁻¹ mg⁻¹ protein) and CL_max (91.3 μL min⁻¹ mg⁻¹ protein) for MBzP formation were comparable to those of DBP hydrolysis. Although the S₅₀ value for MBP formation was comparable to that of MBzP formation, the V_max and CL_max values were markedly lower (<3%) than those for MBzP formation. The S₅₀, V_max and CL_max values for DEHP hydrolysis were 8.40 μM, 0.43 nmol min⁻¹ mg⁻¹ protein and 27.5 μL min⁻¹ mg⁻¹ protein, respectively. The S₅₀ value was about 10% of DBP and BBzP hydrolysis, and the V_max value was also markedly lower (<3%) than those for DBP hydrolysis and MBzP formation for BBzP hydrolysis. The ranking order of CL_max values for monoester phthalate formation in DBP, BBzP and DEHP hydrolysis was BBzP to MBzP ? DBP to MBP > DEHP to MEHP > BBzP to MBP. These findings suggest that the hydrolysis activities of diester phthalates by human liver microsomes depend on the chemical structure, and that the metabolism profile may relate to diester phthalate toxicities, such as hormone disruption and reproductive effects.     

Passive dosing: an approach to control mutagen exposure in the Ames fluctuation test

By using dialysis equilibrium experiments, the sorption of a branched nonylphenol isomer [4-(1-ethyl-1,3-dimethylpentyl)-phenol] (NP111) on various humic acids (HAs) isolated from river sediments and two reference HAs was studied. The HAs were characterized by solid-state ¹³C direct polarization/magic angle spinning nuclear magnetic resonance (¹³C DP/MAS NMR) spectroscopy. Sorption isotherms of NP111 on HAs were described by a linear model. The organic carbon-normalized sorption coefficient (K_OC) ranged from 2.3 × 10³ to 1.5 × 10⁴ L kg⁻¹. Interestingly, a clear correlation between K_OC value and alkyl C content was observed, indicating that the aliphaticity of HAs markedly dominates the sorption of NP111. These new mechanistic insights about the NP111 sorption indicate that the fate of nonylphenols in soil or sediment depends not only on the content of HA, but also on its structural composition.     

Sorption of selected pesticides on soils,sediment and straw from a constructed agricultural drainage ditch or pond

Buffer zones such as ponds and ditches are used to reduce field-scale losses of pesticides from subsurface drainage waters to surface waters. The objective of this study was to assess the efficiency of these buffer zones, in particular constructed wetlands, focusing specifically on sorption processes. We modelled the sorption processes of three herbicides [2-methyl-4-chlorophenoxyacetic acid (2,4-MCPA), isoproturon and napropamide] and three fungicides (boscalid, prochloraz and tebuconazole) on four substrates (two soils, sediment and straw) commonly found in a pond and ditch in Lorraine (France). A wide range of Freundlich coefficient (K _fads) values was obtained, from 0.74 to 442.63 mg^1???n ?L ⁿ ?kg^?1, and the corresponding K _foc values ranged from 56 to 3,725 mg^1???n ?L ⁿ ?kg^?1. Based on potential retention, the substrates may be classified as straw >> sediments > soils. These results show the importance of organic carbon content and nature in the process of sorption. Similarly, the studied pesticides could be classified according to their adsorption capacity as follows: prochloraz >> tebuconazole–boscalid > napropamide >> MCPA–isoproturon. This classification is strongly influenced by the physico-chemical properties of pesticides, especially solubility and K _oc. Straw exhibited the largest quantity of non-desorbable pesticide residues, from 12.1 to 224.2 mg/L for all pesticides. The presence of plants could increase soil–sediment sorption capacity. Thus, establishment and maintenance of plants and straw filters should be promoted to optimise sorption processes and the efficiency of ponds and ditches in reducing surface water pollution.     

Influence of meteorological factors and polluting environment on rain chemistry and wet deposition in a rural area near Chimay,Belgium

This paper focuses on a detailed analysis of the effects of meteorological factors explaining the variability of rain composition.Inorganic composition of 113 individual rain events was measured from May 2002 to October 2005 at a rural site near Chimay, in the western part of the Belgian Ardennes. Original models were fitted for each studied ion (H⁺, Mg²⁺, Ca²⁺, K⁺, NH₄⁺, Na⁺, Cl⁻, NO₃⁻ and SO₄²⁻) to relate rain event concentration or wet deposition to the rainfall volume (R), the length of the antecedent dry period (ADP), the volume of the previous event (R_prev) as well as to the mean wind speed and the prevailing wind direction during both the dry and the rainy periods. These variables explained from 32% (H⁺) to 69% (NO₃⁻) of rain concentration variability. Concentrations decreased logarithmically with increasing R values except in case of H⁺ for which a positive effect of rain volume on rain concentration was observed. ADP affected positively rain concentrations of all ions excluding K⁺ and H⁺ for which, respectively, a nonsignificant and a negative effect of this variable was observed. Increasing R_prev strengthened the effect of the variable R on H⁺, Mg²⁺, Ca²⁺, Na⁺, NH₄⁺ and SO₄²⁻ concentrations while it softened the effect of ADP on NO₃⁻ concentrations. Wind speed and direction during dry and rainy periods explained together from 8% (K⁺) to 38% (Na⁺) of rain concentration total variability. R² coefficients of the wet deposition models ranged from 0.51 (K⁺) to 0.79 (SO₄²⁻). For all ions, wet deposition increased significantly with increasing R values while the effects of the other variables were similar to those on concentrations. Wind conditions during dry and rainy periods explained from 4% (H⁺) to 24% (Na⁺) of wet deposition total variability. On an annual scale, the total dry period duration, the total rainfall volume as well as the shape of the distributions of the length of the antecedent dry periods and of the rain event volume are important parameters that influence annual wet deposition.     

Formation of submicron sulfate and organic aerosols in the outflow from the urban region of the Pearl River Delta in China

Size-resolved chemical compositions of non-refractory submicron aerosols were measured using a quadrupole Aerodyne aerosol mass spectrometer at a rural site near Guangzhou in the Pearl River Delta (PRD) of China in the summer of 2006. Two cases characterized as the outflows from the PRD urban region with plumes of high SO₂ concentration were investigated. The evolution of sulfate size distributions was observed on a timescale of several hours. Namely mass concentrations of sulfate in the condensation mode (with vacuum aerodynamic diameters (D_va) < 300 nm) increased at a rate of about 0.17–0.37 ppbv h^?1 during the daytime. This finding was consistent with the sulfuric acid production rates of about 0.17–0.3 ppbv h^?1, as calculated from the observed gas-phase concentrations of OH (～3.3 × 10⁶–1.7 × 10⁷ cm^?3) and SO₂ (～3–21.2 ppbv). This implies that the growth of sulfate in the condensation mode was mainly due to gas-phase oxidation of SO₂. The observed rapid increase was caused mainly by the concurrent high concentrations of OH and SO₂ in the air mass. The evolution of the mass size distributions of m/z 44, a tracer for oxygenated organic aerosol (OOA), was very similar to that of sulfate. The mass loadings of m/z 44 were strongly correlated with those of sulfate (r² = 0.99) in the condensation mode, indicating that OOA might also be formed by the gas-phase oxidation of volatile organic compound (VOC) precursors. It is likely that sulfate and OOA were internally mixed throughout the whole size range in the air mass.