Application of ultrasonic assisted extraction of chemically diverse organic compounds from soils and sediments

The objective of this research was the development, optimization, and demonstration of an ultrasonic assisted extraction (UAE) based method for organic anthropogenic waste indicators (AWIs) with a range of physicochemical properties from soil and sediment samples. The optimized method was designed to be cost effective compared to existing extraction methods, which may require large quantities of consumables, produce substantial volumes of organic waste, or require costly instrumentation or equipment. Reagent grade sand, soil collected from the native grassland in proximity to Eastern Washington University (EWU), and sediment samples collected from the Spokane river were used as sample matrices during method development. These matrices were fortified with eight AWIs of varying chemical properties that are representative of a variety of household, industrial, and agricultural sources. The recoveries of the AWIs spiked onto these matrices were determined in the extracts using gas chromatography/mass spectrometry (GC/MS). These values reflect the efficiency of the method for extraction of these analytes from representative environmental matrices. Recoveries ranged from 46.1% to 110% in the fortified soil and from 49.2% to 118.6% in the fortified sediment samples, which is comparable with existing methods for the study analytes. The optimized method was then used to quantify AWIs in a biosolid-amended soil. Indole and p-cresol were detected in the biosolid-amended soil.     

Concentrations and specific loads of brominated flame retardants in sewage sludge

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. The present study focuses on two classes of brominated flame retardants: polybrominated diphenyl ethers (BDE28, BDE47, BDE49, BDE66, BDE85, BDE99, BDE100, BDE119, BDE138, BDE153, BDE154, BDE183, BDE209) and hexabromocyclododecane (HBCD) detected in sewage sludge collected from a monitoring network in Switzerland. Mean concentrations (n=16 wastewater treatment plants) were 310, 149, 95 and 17microg per kg dry matter for decaBDE, HBCD, penta- and octaBDE, respectively. These numbers correspond well with other studies from European countries. DecaBDE, HBCD, penta- and octaBDE showed average specific loads (load per connected inhabitant per year) in sludge of 6.1, 3.3, 2.0 and 0.3mgcap(-1)yr(-1), respectively. This is in line with consumption and storage of the compounds in the environment and the anthroposphere. Discrepancies observed for octaBDE and HBCD can be explained by the release from materials where these compounds are incorporated in and/or their degradation during anaerobic sludge treatment. Loads from different types of monitoring sites showed that brominated flame retardants ending up in sewage sludge originate mainly from surface runoff, industrial and domestic wastewater.     

Biodegradability and toxicity assessment of trans-chlordane photochemical treatment

The removal of trans-chlordane (C(10)H(6)Cl(8)) from aqueous solutions was studied using UV, UV/H(2)O(2), UV/H(2)O(2)/Fe(2+), UV/TiO(2), or UV/TiO(2)/H(2)O(2) treatment using either UV/Vis blue lamps or UVC lamps (254 nm). H(2)O(2), FeSO(4) and TiO(2) were added at 1700, 456, and 2500 mgL(-1), respectively. trans-Chlordane was not significantly removed in non-irradiated controls and in samples irradiated with UV/Vis. It was also not removed in the absence of surfactant Triton X-114 added at 250 mgL(-1). In the presence of the surfactant, trans-chlordane concentration was reduced by 95-100% after 48 h of UVC and UVC/H(2)O(2) treatments and 70-80% after UVC/H(2)O(2)/Fe(2+), UVC/TiO(2) and UVC/H(2)O(2)/TiO(2) treatments. Based on these results, UVC, UVC/H(2)O(2) and UVC/TiO(2) treatments were further investigated. UVC treatment supported the highest pollutant removal (100% in 48 h), dechlorination efficiency (81% in 48 h), and detoxification to Lepidium sativum seed germination and activated sludge respiration although irradiated samples remained toxic to Chlorella vulgaris. Biodegradation of the UVC irradiated samples removed the source of algae toxicity but this could not be clearly attributed to the removal of trans-chlordane photoproducts because the surfactant interfered with the chemical and biological assays. Evidence was found that trans-chlordane was photodegraded through photolysis causing its successive dechlorination. trans-Chlordane removal was well described by a first order kinetic model at a rate of 0.21±0.01h(-1) at the 95% confidence interval.     

Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution

The photochemical transformation of natural estrogenic steroid 17beta-estradiol (E2) and the synthetic oral contraceptive 17alpha-ethinylestradiol (EE2) has been studied in dilute non buffered aqueous solution (pH 5.5-6.0) upon monochromatic (254 nm) and polychromatic (lambda>290 nm) irradiation. Upon irradiation at 254 nm, the quantum yields of E2 and EE2 photolysis were similar and evaluated to be 0.067+/-0.007 and 0.062+/-0.007, respectively. Upon polychromatic excitation, and by using phenol as chemical actinometer, the photolysis efficiencies have been determined to be 0.07+/-0.01 and 0.08+/-0.01 for E2 and EE2, respectively. For both estrogens, photodegradation by-products were identified with GC/MS and LC/MS. In a first step, a model compound--5,6,7,8-tetrahydro-2-naphthol (THN)--, which represents the photoactive phenolic group, was used to obtain basic photoproduct structural informations. Numerous primary and secondary products were observed, corresponding to hydroxylated phenolic- or quinone-type compounds.     

The hydrochemistry of groundwater in the Densu River Basin, Ghana

Hydrochemical analyses of groundwater samples were used to establish the hydrochemistry of groundwater in the Densu River Basin. The groundwater was weakly acidic, moderately mineralized, fresh to brackish with conductivity ranging from of 96.6 μS cm^???1 in the North to 10,070 μS cm^???1 in the South. Densu River basin have special economic significance, representing the countries greatest hydrostructure with freshwater. Chemical constituents are generally low in the North and high in the South. The order of relative abundance of major cations in the groundwater is Na^?+??> Ca^2?+??> Mg^2?+??> K^?+? while that of anions is Cl^????> HCO $_{3}^{-} >$ SO $_{4}^{2-} >$ NO $_{3}^{-}$ . Four main chemical water types were delineated in the Basin. These include Ca–Mg–HCO₃, Mg–Ca–Cl, Na–Cl, and mixed waters in which neither a particular cation nor anion dominates. Silicate weathering and ion exchange are probably the main processes through which major ions enter the groundwater system. Anthropogenic activities were found to have greatly impacted negatively on the quality of the groundwater.     

Step-up multiple regression model to compute Chlorophyll a in the coastal waters off Cochin, southwest coast of India

The interaction effects of abiotic processes in the production of phytoplankton in a coastal marine region off Cochin are evaluated using multiple regression models. The study shows that chlorophyll production is not limited by nutrients, but their physiological regulations (responses to nutrients, pH, temperature and salinity) are mainly responsible for the increased biological production. The model explaining 77% of variability for chlorophyll a production is indicative of preconditioning of the coastal waters. The phytoplankton production is found to be sensitive to the environment, which varies seasonally. Further, the study suggests that supply of organic matter and grazing of zooplankton (not included) would improve the model efficiency. Despite this, the good agreement in the computed and measured chlorophyll a values shows that step-up multiple regression model is a useful tool to understand the influence of environmental variables on the production of phytoplankton in these coastal waters.     

Automated riverine landscape characterization: GIS-based tools for watershed-scale research, assessment, and management

River systems consist of hydrogeomorphic patches (HPs) that emerge at multiple spatiotemporal scales. Functional process zones (FPZs) are HPs that exist at the river valley scale and are important strata for framing whole-watershed research questions and management plans. Hierarchical classification procedures aid in HP identification by grouping sections of river based on their hydrogeomorphic character; however, collecting data required for such procedures with field-based methods is often impractical. We developed a set of GIS-based tools that facilitate rapid, low cost riverine landscape characterization and FPZ classification. Our tools, termed RESonate, consist of a custom toolbox designed for ESRI ArcGIS®. RESonate automatically extracts 13 hydrogeomorphic variables from readily available geospatial datasets and datasets derived from modeling procedures. An advanced 2D flood model, FLDPLN, designed for MATLAB® is used to determine valley morphology by systematically flooding river networks. When used in conjunction with other modeling procedures, RESonate and FLDPLN can assess the character of large river networks quickly and at very low costs. Here we describe tool and model functions in addition to their benefits, limitations, and applications.