The role of organic ligands in ferrous-induced photochemical degradation of 2,4-dichlorophenoxyacetic acid

Recent studies have shown that hydrogen peroxide is generated in a ferrioxalate-induced photoreductive reaction, but information about the effect of organic ligands on the photochemical behaviour of ferrous species is limited. The degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by a ferrous-catalyzed oxidation in the presence of various ligands such as formate, citrate, malelate, oxalate, and ethylenediaminetetra-acetic acid (EDTA) was studied. The experiments were conducted under either dark or irradiated (350n m) conditions. Forty-two percent and 34% of 2,4-D were removed by the Fe(2+)/oxalate/UV and Fe(2+)/citrate/UV processes, respectively, after 30 min of reaction and oxidative intermediates were obtained in both cases. The presence of hydroxylated intermediates suggests that 2,4-D may be attacked by hydroxyl radicals, which are the products of the photo-Fenton-like reaction. As such, hydrogen peroxide was produced by the photolysis of ferrous oxalate or ferrous citrate, referred to hereafter as photogenerated H(2)O(2). As expected, the total removal percentage of 2,4-D jumped to 97% when 1mM of hydrogen peroxide (so-called spiked H(2)O(2)) was externally added to the reaction vessel to initiate the Fe(2+)/oxalate/UV process. Therefore, the treatment of 2,4-D by the Fe(2+)/oxalate/H(2)O(2)/UV system can be operated in two steps: the photolysis of ferrous oxalate first, followed by adding the spiked H(2)O(2) sometime after the commencement of the reaction. A two-phase model has been developed to describe this tandem ferrous-catalyzed photooxidation, which would help to achieve the mineralization of 2,4-D.     

Physicochemical properties of chars at different treatment temperatures

In this study, the physicochemical properties of the char of Indonesian SM coal following heat treatment at various temperatures were evaluated using X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and morphological and specific surface area analysis. Based on these analyses, heat treatment of coal was determined to be the most effective in increasing the coal rank. In the XPS analysis, the C–O and C–O–C groups and quaternary-N species were found to be of a lower grade coal when the pretreatment temperature decreased, meanwhile the C–C group and pyridinic species increased. In the FT-IR analysis, the collapse of the C–O and C–O–C group was observed due to the collapse of the ether group. In SEM and Brunauer–Emmett–Teller (BET) analysis, a decrease in the ether group was shown to be accompanied with the formation of micropores.

Implications Recently, XPS analyses have been reported as coal surface analysis. Usually, they have reported the analysis of the coals with different rank. This study investigated the coal surface characteristics of the coals pretreated at different temperature using various analyses (BET, SEM, XPS, FT-IR), and this study can be the basis for other research and applications.     

A phenomenographical approach to the study of pre-adolescents' use of maps in a wayfinding exercise in a suburban environment

This paper reports the investigative study, which used a phenomenographical approach, on how a group of 12-year-old students found their way around a designated suburban route by referring to a sequential listing of streets along the route and a street directory map of the suburban area. While the content of this study belongs to map use and wayfinding experience of the pre-adolescent students, the approach used is phenomenographic in that it identified the qualitatively different ways that the students experienced the suburban environment. The students' experiences were interpreted using a behaviourial matrix of their actions while they traversed the route. Qualitative variations in their approaches to wayfinding using maps were obtained from interviews which were conducted immediately after the students completed their route navigation. Four qualitatively different approaches were determined from their reflections of their own wayfinding behaviours. They are the restricted and neophytic approach; careful and sequential approach; deductive and familiarized approach; and the visualized and co-ordinated spatial approach. These approaches reflect the different behaviours and abilities of the students to: plan their route using a street directory map; plan the route street by street or a number of streets at a time; use street signs and other landmarks during the actual task; utilize local knowledge of the route; maintain their orientation; visualize spatial patterns; and use the scale on the map to help planning.     

Metal Contamination in Zebra Mussels (Dreissena Polymorpha) Along the st. Lawrence River

In order to evaluate the use of zebra mussels as biomonitors for metal bioavailability in the St. Lawrence River, we tested the hypothesis that the concentrations of 11 metals in zebra mussels vary significantly between sites along the river and that the season of collection and body size affect metal bioaccumulation. Mussels were collected at 14 sites during June 1996 and at monthly intervals at one site. Specimens were grouped in three size classes and their soft tissue was analyzed for As, Ca, Cd, Cr, Hg, Mn, Ni, Pb, Se, and Zn. Significant size effects were found for Ca, Cd, Cr, Cu, Ni and Zn. Spatial and seasonal variations in bioconcentration were significant for all metals. Spatial patterns in contamination that corresponded to known point sources of pollution or hydrology of the river were identified by principal component analysis. Seasonal variations can be attributed to the reproductive cycle of mussels and hydrological variability of the river. In comparison with values reported for zebra mussels in other contaminated sites in North America and Europe, levels of metal in the St. Lawrence River are low or intermediate. Our results show that when controlled for size and seasonal effects, zebra mussels represent a useful biomonitor for metal availability in the river and may offer an interesting alternative to native mussels and fish for such a role. Local contamination by some toxic metals is still a cause for concern in the St. Lawrence River.     

Study of the PM<Subscript>10</Subscript> concentration variations along two intra-urban roads within a compact city

Eighty-five measurement campaigns were performed repeatedly to compare the concentration variation profiles along two intra-urban roads—one with open configuration and the other with street canyon effect. Fixed-effects panel data analysis was applied for formulating a model to express the PM₁₀ concentrations along intra-urban roads in terms of parameters like nearby central monitoring data, traffic counts and meteorological conditions with an objective to analyze the PM₁₀ concentration variation patterns along the two roads. Our findings reveal that traffic intensity and metrological conditions exert influence on concentration variation for both types of road configurations while wind velocity only affect the pollutants removal effectiveness of open road configuration. Further analysis unveils that the PM₁₀ concentration distribution profiles within a compact city environment are not always uniform and are dependent on the road configuration. Considerable PM₁₀ concentration differences were observed along the street canyon, and 70% of their variations are attributed to variations in their road aspect ratios. By contrast, no significant concentration difference is observed at open road configurations.     

Effect of data pre-treatment procedures on principal component analysis: a case study for mangrove surface sediment datasets

Principal component analysis (PCA) is capable of handling large sets of data. However, lack of consistent method in data pre-treatment and its importance are the limitations in PCA applications. This study examined pre-treatments methods (log (x?+?1) transformation, outlier removal, and granulometric and geochemical normalization) on dataset of Mengkabong Lagoon, Sabah, mangrove surface sediment at high and low tides. The study revealed that geochemical normalization using Al with outliers removal resulted in a better classification of the mangrove surface sediment than that outliers removal, granulometric normalization using clay and log (x?+?1) transformation. PCA output using geochemical normalization with outliers removal demonstrated associations between environmental variables and tides of mangrove surface sediment, Mengkabong Lagoon, Sabah. The PCA outputs at high and low tides also provided to better interpret information about the sediment and its controlling factors in the intertidal zone. The study showed data pre-treatment method to be a useful procedure to standardize the datasets and reducing the influence of outliers.     

Prenatal diagnosis of Myhre syndrome with a heterozygous pathogenic variant in SMAD4 gene presented with thick nuchal translucency and cardiac abnormalities

Prenatal testing was performed in a 39-year-old Chinese pregnant woman referred for increased nuchal translucency measuring 5.7 mm. Non-invasive prenatal testing and SNP array study on amniotic fluid samples were normal. Whole exome sequencing (WES) was initiated further as the fetus had pericardial effusion of 1.2 mm, thickened myocardium over the right ventricular lateral wall and aberrant right subclavian artery. A detailed fetal echocardiogram also revealed persistent left superior vena cava and dilated coronary sinus at 20 weeks. From whole exome sequencing of the trio, a de novo heterozygous variant NM_005359.5(SMAD4): c.1499T>C (p.Ile500Thr) was detected. This pathogenic variant has been reported in the postnatal case cohort of Myhre syndrome. This condition is characterized by facial dysmorphism, intellectual disability, hearing loss, skeletal abnormalities and potential life threatening respiratory or cardiovascular manifestations. Termination of pregnancy was performed at 23 weeks. Small chins, pre-axial polydactyly, brachydactyly and clinodactyly were noted in the abortus. Ultrasound findings of increased nuchal translucency, thickened myocardium and pericardial effusion prompted further genetic evaluation for the prenatal diagnosis of Myhre syndrome by whole exome sequencing.     

Observed chemical characteristics of long-range transported particles at a marine background site in Korea

Deokjeok Island is located off the west coast of the Korean Peninsula and is a suitable place to monitor the long-range transport of air pollutants from the Asian continent. In addition to pollutants, Asian dust particles are also transported to the island during long-range transport events. Episodic transport of dust and secondary particles was observed during intensive measurements in the spring (March 31-April 11) and fall (October 13-26) of 2009. In this study, the chemical characteristics of long-range-transported particles were investigated based on highly time-resolved ionic measurements with a particle-into-liquid system coupled with an online ion chromatograph (PILS-IC) that simultaneously measures concentrations of cations (Li+, Na , NH4+, K+, Ca2+, Mg2+) and anions (F-, C1-, NO3-, SO42-). The aerosol optical thickness (AOT) distribution retrieved by the modified Bremen Aerosol Retrieval (M-BAER) algorithm from moderate resolution imaging spectroradiometer (MODIS) satellite data confirmed the presence of a thick aerosol plume coming from the Asian continent towards the Korean peninsula. Seven distinctive events involving the long-range transport (LRT) of aerosols were identified and studied, the chemical components of which were strongly related to sector sources. Enrichment of acidic secondary aerosols on mineral dust particles, and even of sea-salt components, during transport was observed in this study. Backward trajectory, chemical analyses, and satellite aerosol retrievals identified two distinct events: a distinctively high [Ca2++Mg2]/[Na+] ratio (>2.0), which was indicative of a preprocessed mineral dust transport event, and a low [Ca2++Mg2+]/[Na+] ratio (<2.0), which was indicative of severe aging of sea-salt components on the processed dust particles. Particulate C1- was depleted by up to 85% in spring and 50% in the fall. A consistent fraction of carbonate replacement (FCR) averaged 0.53 in spring and 0.55 in the fall. Supporting evidences of C1- enrichment on the marine boundary layer prior to a dust front were also found. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for sector and air mass classifications of clean and LRT cases.     

Extricating Membership as a PRP at Hazardous Waste Disposal Sites

Corporations often become potentially responsible parties (PRPs) at hazardous waste sites because of their past transportation or disposal of hazardous substances at such sites. Determining a PRP's potential liability for the assessment and cleanup of hazardous waste sites is a challenging effort and often results in disputes among other PRPs regarding appropriate allocation of response action costs to each party. Further, public companies have an obligation to report probable and reasonably estimable costs under Generally Accepted Accounting Principles (GAAP) for environmental liabilities at their current or prior hazardous waste sites. The first step in such an evaluation is to determine whether or not a PRP can extricate themselves from any association with the subject site or, alternatively, demonstrate de minimis status. This article describes the methods by which PRPs can extricate themselves from liability associated with response action costs at contaminated sites, including: evaluating a PRP's prior settlements or indemnifications with other PRPs; identifying insurance coverage or other financial assurance instruments for the disposal facility; and examining applicable statutes of limitations against when a PRP received notification from the regulatory agency. The article also presents a case study discussing how a PRP with a portfolio of 72 hazardous waste disposal sites was able to extricate itself from the majority of these sites, resulting in only four sites where the PRP was determined to be a PRP and where an associated allocable share was assigned. © 2014 Wiley Periodicals, Inc.