Determination of o-phthalic acid in snow and its photochemical degradation by capillary gas chromatography coupled with flame ionization and mass spectrometric detection

Phthalic acid and its photochemical degradation has been determined in snow and rainwater samples collected during winters (2003-2010) in the Southeast of Massachusetts using capillary gas chromatography (GC) with flame ionization and mass spectrometric detection. Water samples were dried using a rotary evaporator and derivatized with a 14% BF₃/methanol reagent before GC analysis. The developed method proved simple and accurate. Phthalic acid was found in snow samples collected in a concentration range of 7.22-76.5 nM. The photodegradation of phthalate was carried out under 300 nm UV light. The direct photodecomposition of the acid is slow (5% h⁻¹). However, the addition of dissolved Fe(III) species at 2.0 μM accelerated the light-induced degradation of phthalic acid by 3.5 times in the atmospheric water samples. Photodegradation rates of phthalic acid increases with decreasing pH value of water samples in the range of pH 2.8-4.5.     

Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g⁻¹ dry weight (dw) (mean: 24.7 pg g⁻¹ dw) in Jiaozhou Bay, <1.2 to 135 pg g⁻¹ dw (mean 69.9 pg g⁻¹ dw) in Sishili Bay and <1.2 to 66.7 pg g⁻¹ dw (mean: 40.4 pg g⁻¹ dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6-5.1% of the ∑DP concentration.The f_syn values (syn-isomer/(syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2-0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f_syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

Mass flows of perfluorinated compounds (PFCs) in central wastewater treatment plants of industrial zones in Thailand

Perfluorinated compounds (PFCs) are fully fluorinated organic compounds, which have been used in many industrial processes and have been detected in wastewater and sludge from municipal wastewater treatment plants (WWTPs) around the world. This study focused on the occurrences of PFCs and PFCs mass flows in the industrial wastewater treatment plants, which reported to be the important sources of PFCs. Surveys were conducted in central wastewater treatment plant in two industrial zones in Thailand. Samples were collected from influent, aeration tank, secondary clarifier effluent, effluent and sludge. The major purpose of this field study was to identify PFCs occurrences and mass flow during industrial WWTP. Solid-phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis. Total 10 PFCs including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluoropropanoic acid (PFPA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonate (PFHxS), perfluoronanoic acid (PFNA), perfluordecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA) were measured to identify their occurrences. PFCs were detected in both liquid and solid phase in most samples. The exceptionally high level of PFCs was detected in the treatment plant of IZ1 and IZ2 ranging between 662-847 ng L⁻¹ and 674-1383 ng L⁻¹, respectively, which greater than PFCs found in most domestic wastewater. Due to PFCs non-biodegradable property, both WWTPs were found ineffective in removing PFCs using activated sludge processes. Bio-accumulation in sludge could be the major removal mechanism of PFCs in the process. The increasing amount of PFCs after activated sludge processes were identified which could be due to the degradation of PFCs precursors. PFCs concentration found in the effluent were very high comparing to those in river water of the area. Industrial activity could be the one of major sources of PFCs contamination in the water environment.     

Performance of photocatalytic lamps on reduction of culturable airborne microorganism concentration

Reduction of viable airborne Staphylococcus epidermidis and Aspergillus niger spore concentrations using two types of photocatalytic fluorescent lamps under controlled environmental conditions (25 vs. 35 °C and 55 vs. 75% relative humidity) were investigated. Visible white-light and UVA black light were in-house spray-coated with TiO₂ and then compared with a commercially coated visible white-light for microbial concentration reduction. The white-light photocatalytic lamps reduced the concentration of culturable S. epidermidis up to 92% independent of temperature or humidity change, while the black light photocatalytic lamps completely inactivated the culturable bacteria at 25 °C, 55% relative humidity. Humidity seemed to alleviate UVA damage since better bacteria survival was found. For A. niger spores, rising humidity or temperature could lower their concentration or drop their culturabilities so that a difference between the natural decay and photocatalytic disinfection could not be distinguished. Reductions of total bacteria and total fungi concentrations using these lamps were also examined under uncontrolled environmental conditions in an office and a waste-storage room. It was found that photocatalytic lamps could reduce total culturable bacteria concentration from 9 to 97% and total culturable fungi concentration from 3 to 95% within irradiation time of 30-480 min, respectively. Insignificant difference in concentration reduction among these photocatalytic lamps was pronounced.     

Acute toxicity, biochemical and gene expression responses of the earthworm Eisenia fetida exposed to polycyclic musks

Phytoremediation is a novel and promising approach for the treatment of pollutants. This study did explore the potential of Aster amellus Linn. to decolorize a sulfonated azo dye Remazol Red (RR), a mixture of dyes and a textile effluent. Induction in the activities of lignin peroxidase, tyrosinase, veratryl alcohol oxidase and riboflavin reductase was observed during RR decolorization, suggesting their involvement in the metabolism of RR. UV-Visible absorption spectrum, HPLC and FTIR analysis confirmed the degradation of RR. Four metabolites after the degradation of the dye were identified as 2-[(3-diazenylphenyl) sulfonyl] ethanesulfonate, 4-amino-5-hydroxynaphthalene-2,7-disulfonate, naphthalene-2-sulfonate and 3-(1,3,5-triazin-2-ylamino)benzenesulfonate by using GC/MS. Textile effluent and mixture of dyes showed 47% and 62% decrease respectively in American Dye Manufacturers Institute value. BOD of textile effluent and mixture of dyes were reduced by 75% and 48% respectively, COD of industrial effluent and mixture of dyes was reduced by 60% and 75% and TOC was reduced by 54% and 69% respectively after the treatment by A. amellus for 60 h; this indicated that the plant can be used for cleaning textile effluents. Toxicity study revealed the phytotransformation of RR into non-toxic products.     

Probability of intellectual disability is associated with soil concentrations of arsenic and lead

Background

The association between metals in water and soil and adverse child neurologic outcomes has focused on the singular effect of lead (Pb), mercury (Hg), and arsenic (As). This study describes the complex association between soil concentrations of As combined with Pb and the probability of intellectual disability (ID) in children.

Methods

We used a retrospective cohort design with 3988 mother child pairs who were insured by Medicaid and lived during pregnancy and early childhood in South Carolina between 1/1/97 and 12/31/02. The children were followed until 6/1/08, using computerized service files, to identify the diagnosis of ID in medical records and verified by either school placement or disability service records. The soil was sampled using a uniform grid and analyzed for eight metals. The metal concentrations were interpolated using Bayesian Kriging to estimate concentration at individual residences.

Results

The probability of ID increased for increasing concentrations of As and Pb in the soil. The Odds Ratio for ID, for one unit change in As was 1.130 (95% confidence interval 1.048-1.218) for Pb was 1.002 (95% confidence interval 1.000-1.004). We identified effect modification for the infants based on their birth weight for gestational age status and only infants who were normal size for their gestational age had increased probability of ID based on the As and Pb soil concentrations (OR for As at normal weight for gestational age = 1.151 (95% CI: 1.061-1.249) and OR for Pb at normal for gestational age = 1.002 (95% CI: 1.002-1.004)). For normal weight for gestational age children when As = 22 mg kg⁻¹ and Pb = 200 mg kg⁻¹ the risk for ID was 11% and when As = 22 mg kg⁻¹and Pb = 400 mg kg⁻¹ the probability of ID was 65%.

Conclusion

The probability of ID is significantly associated with the interaction between Pb and As for normal weight for gestational age infants.     

A level change in mutagenicity of Japanese tap water over the past 12 yr

A relative comparison study of mutagenicity in Japanese tap water was conducted for 1993 and 2005 surveys. It intended to assess the effects of advanced water treatment installations to water works, improvement of raw water quality and improvement of residual HOCl concentration controlling. Sampling points (taps) were the same in both surveys. The results of 245 samples obtained by the Ames Salmonella mutagenicity test (Ames test) were analyzed. The Ames tests were conducted by using Salmonella typhimurium TA98 and TA100 strains with and without exogenous activation (S9). With the exception of TA100-S9, the other conditions needed no discussion as a factor in the mutagenicity level change. The average mutagenicity in 1993 and 2005 under the conditions of TA100-S9 were 2600 and 1100 net revertant L⁻¹, respectively. This indicated that the mutagenicity level of Japanese tap water decreased during the 12-yr period. Particularly a remarkable decrease in mutagenicity was observed in the water works where the advanced water treatments were installed during the 12-yr period. The advanced water treatments were effective in decreasing the mutagenicity of tap water. Mutagenicity also decreased in the water works with conventional water treatments; the improvement of residual HOCl concentration controlling was also considered to be effective in decreasing the mutagenicity of tap water.     

Interactions between accumulation of trace elements and macronutrients in Salix caprea after inoculation with rhizosphere microorganisms

Although the beneficial effects on growth and trace element accumulation in Salix spp. inoculated with microbes are well known, little information is available on the interactions among trace elements and macronutrients. The main purpose of this study was to assess the effect of phytoaugmentation with the rhizobacteria Agromyces sp., Streptomyces sp., and the combination of each of them with the fungus Cadophora finlandica on biomass production and the accumulation of selected trace elements (Zn, Cd, Fe) and macronutrients (Ca, K, P and Mg) in Salix caprea grown on a moderately polluted soil. Dry matter production was significantly enhanced only upon inoculation with Agromyces sp. Regarding the phytoextraction of Cd and Zn, shoot concentrations were mostly increased after inoculation with Streptomyces sp. and Agromyces sp. + C. finlandica. These two treatments also showed higher translocation factors from roots to the leaves for both Cd and Zn. The accumulation of Cd and Zn in shoots was related to increased concentrations of K. This suggests that microorganisms that contribute to enhanced phytoextraction of Cd and Zn affect also the solubility and thus phytoavailability of K. This study suggests that the phytoextraction of Zn and Cd can be improved by inoculation with selected microbial strains.     

Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.