Toxicity and biodegradation of diamines

Phytotoxicity and cytotoxicity of 2,4-diaminotoluene (2,4-D), 4,4'-methylenedianiline (4,4-D), and 1,6-hexanediamine (1,6-D) were investigated by observing the germination of young radish seeds and the viability of HeLa cells, respectively. 2,4-D showed the highest, 4,4-D intermediate, and 1,6-D lowest cytotoxicity. However, the phytotoxicity decreased in the order of 4,4-D > 2,4-D > 1,6-D. Contrary to the results previously reported, in the modified Sturm test the activated sludge degraded 2,4-D and 4,4-D as well as 1,6-D without any pre-acclimation. Ochrobacterium antropi was isolated for degradation of 2,4-D and 4,4-D and Pseudomonas citronellolis for 1,6-D degradation. Thielevia sp. was isolated as 2,4-D degrading fungus and Aspergillus sp. as 4,4-D and 1,6-D degrading fungus. The fungi degraded the diamines faster than the bacteria.     

Formation of dimethyldithioarsinic acid in a simulated landfill leachate in relation to hydrosulfide concentration

Dimethyldithioarsinic acid (DMDTA^V), present in such intense sources as municipal landfill leachate, has drawn a great deal of attention due to its abundant occurrence and different aspect of toxicity. The hydrosulfide (HS⁻) concentration in leachate was studied as a major variable affecting the formation of DMDTA^V. To this end, the HPLC–ICPMS system equipped with the reversed-phase C18 column was used to determine DMDTA^V. Simulated landfill leachates (SLLs) were prepared to cover a mature landfill condition with the addition of sodium sulfate and sulfide at varying concentrations in the presence of dimethylarsinic acid (DMA^V). The concentration of sodium sulfide added in the SLLs generally exhibited a strong positive correlation with the concentration of DMDTA^V. As such, the formation of DMDTA^V in the SLLs is demonstrated to be controlled by the interactive relationship between DMA^V and the HS⁻.

     

Physical Properties of Chemically Modified Starch(RS4)/PVA Blend Films—Part 1

In this paper, we report on the physical properties of films that have been synthesized by using native corn starch (NS) and chemically modified starch (RS4). NS or RS4/PVA blend films were synthesized by using the mixing process and the casting method. Glycerol (GL), sorbitol (SO), and citric acid (CA) were used as additives. The chemically modified starch (RS4) was synthesized by using sodium trimetaphosphate (STMP) and sodium tripolyphosphate (STPP) as a crosslinker. Then, the RS4 thus synthesized was confirmed by using the pancreatin-gravimetric method, swelling power and an X-ray diffractometer (XRD). Tensile strength (TS), elongation (%E), swelling behavior (SB), and solubility (S) of the films were measured. The result of the measurements indicated the RS4-added film was better than the NS-added film. Especially, the RS4/PVA blend film with CA as an additive showed the physical properties superior to other films.     

Evidence of singlet oxygen and hydroxyl radical formation in aqueous goethite suspension using spin-trapping electron paramagnetic resonance (EPR)

The generation of reactive species in an aqueous goethite suspension, under room light and aeration conditions, was investigated using the electron paramagnetic resonance (EPR) technique employing spin trap agents. The trap reagents, including 5,5-dimethylpyrroline N-oxide (DMPO) and 2,2,6,6-tetramethylpiperidine (TEMP), were used for the detection of OH radicals (OH) and singlet oxygen (¹O₂), respectively. On the addition of DMPO to the goethite suspended solution, a DMPO-OH adduct was formed, which was not decreased, even in the presence of the OH scavenger, mannitol. This result implied a false positive interpretation from the DMPO-OH EPR signal. In the presence of TEMP reagent, a TEMP-O signal was detected, which was completely inhibited in the presence of the singlet oxygen scavenger, sodium azide. With both DMPO-OH and TEMP-O radicals in the presence and absence of radical scavengers, singlet oxygen was observed to be the key species formed in the room-light sensitized goethite suspension. In the goethite/H₂O₂ system; however, both OH and singlet oxygen were generated, with significant portions of DMPO-OH resulting from both OH and singlet oxygen. In fact, the DMPO-OH resulting from OH should be carefully calculated by correcting for the amount of DMPO-OH due to singlet oxygen. This study reports, for the first time, that the goethite suspensions may also act as a natural sensitizer, such as fulvic acids, to form singlet oxygen.     

Predictions of long-term performance of granular iron permeable reactive barriers: field-scale evaluation

Long-term performance is a key consideration for the granular iron permeable reactive barrier (PRB) technology because the economic benefit relies on sustainable operation for substantial periods of time. However, predictions on the long-term performance have been limited mainly because of the lack of reliable modeling tools. This study evaluated the predictive capability of a recently-developed reactive transport model at two field-scale PRBs, both having relatively high concentrations of dissolved carbonate in the native groundwater. The first site, with 8 years of available monitoring data, was a funnel-and-gate installation, with a low groundwater velocity through the gate (about 0.12 m d(-1)). The loss in iron reactivity caused by secondary mineral precipitation was small, maintaining relatively high removal rates for chlorinated organics. The simulated concentrations for most constituents in the groundwater were within the range of the monitoring data. The second site, with monitoring data available for 5 years, was a continuous wall PRB, designed for a groundwater velocity of 0.9 m d(-1). A comparison of measured and simulated aqueous concentrations suggested that the average groundwater velocity through the PRB could be lower than the design value by a factor of two or more. The distribution and amounts of carbonate minerals measured in core samples supported the decreased groundwater velocity used in the simulation. The generally good agreement between the simulated and measured aqueous and solid-phase data suggest that the model could be an effective tool for predicting long-term performance of granular iron PRBs, particularly in groundwater with high concentrations of carbonate.     

Effect of incineration on the removal of key offensive odorants released from a landfill leachate treatment station (LLTS)

As a basic means to control odorants released from a landfill leachate treatment station (LLTS), effluents venting from this station were treated via incineration with methane rich landfill gas (at 750 °C). A list of the key offensive odorants covering 22 chemicals was measured by collecting those gas samples both before and after the treatment. Upon incineration, the concentration levels of most odorants decreased drastically below threshold levels. The sum of odorant intensities (SOIs), if compared between before and after incineration, decreased from 6.94 (intolerable level) to 3.45 (distinct level). The results indicate that the thermal incineration method can be used as a highly efficient tool to remove most common odorants (e.g., reduced sulfur species), while it is not so for certain volatile species (e.g., carbonyls, fatty acids, etc.).     

Biodegradability of Chemically Modified Starch (RS4)/PVA Blend Films: Part 2

Biodegradable films were successfully prepared by using cornstarch (CS), chemically modified starch (RS4), polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA). The physical properties and biodegradability of the films using CS, RS4, and additives were investigated. The results of the investigation revealed that the RS4-added film was better than the CS-added film in tensile strength (TS), elongation at break (%E), swelling behavior (SB) and solubility (S). Especially, the RS4/PVA blend film with CA as an additive showed physical properties superior to other films. Furthermore, when the film was dried at low temperature, the properties of the films clearly improved because the hydrogen bonding was activated at low temperature. The biodegradation of films was carried out using the enzymatic, microbiological and soil burial test. The enzyme used in this study was amyloglucosidase (AMG), α-amylase (α-AM) and β-amylase (β-AM). At the enzymatic degradation test, the GL-added films had an approximately 60% degradation, while the CA-added films were degraded about 25%. The low degradation value on CA-added film is attributed to low pH of film added CA that deactivated the enzymatic reaction. The microbiological degradation teat was performed by using Bacillus subtilis and Aspergillus niger.     

Grazing management effects on sediment, phosphorus, and pathogen loading of streams in cool-season grass pastures

Erosion and runoff from pastures may lead to degradation of surface water. A 2-yr grazing study was conducted to quantify the effects of grazing management on sediment, phosphorus (P), and pathogen loading of streams in cool-season grass pastures. Six adjoining 12.1-ha pastures bisected by a stream in central Iowa were divided into three treatments: continuous stocking with unrestricted stream access (CSU), continuous stocking with restricted stream access (CSR), and rotational stocking (RS). Rainfall simulations on stream banks resulted in greater ( < 0.10) proportions of applied precipitation and amounts of sediment and P transported in runoff from bare sites than from vegetated sites across grazing treatments. Similar differences were observed comparing vegetated sites in CSU and RS pastures with vegetated sites in CSR pastures. Bovine enterovirus was shed by an average of 24.3% of cows during the study period and was collected in the runoff of 8.3 and 16.7% of runoff simulations on bare sites in CSU pastures in June and October of 2008, respectively, and from 8.3% of runoff simulations on vegetated sites in CSU pastures in April 2009. Fecal pathogens (bovine coronavirus [BCV], bovine rotavirus group A, and O157:H7) shed or detected in runoff were almost nonexistent; only BCV was detected in feces of one cow in August of 2008. Erosion of cut-banks was the greatest contributor of sediment and P loading to the stream; contributions from surface runoff and grazing animals were considerably less and were minimized by grazing management practices that reduced congregation of cattle by pasture streams.     

Mechanism for the stabilization/solidification of arsenic-contaminated soils with Portland cement and cement kiln dust

In this study, the mechanism for the stabilization/solidification (S/S) of arsenic (As)-contaminated soils with Portland cement (PC), and cement kiln dust (CKD) using 1 N HCl extraction fluid, X-ray powder diffraction (XRPD), X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS) spectroscopy was investigated. The degree of As immobilization after stabilization was assessed using a 1 N HCl extraction on the basis of the Korean Standard Test (KST). After 1 day of curing with 30 wt% PC and 7 days of curing with 50 wt% CKD, the concentration of As leached from the amended soils was less than the Korean countermeasure standard (3 mg L^?1). The As concentrations in the leachate treated with PC and CKD were significantly decreased at pH > 3, indicating that pH had a prevailing influence on As mobility. XRPD results indicated that calcium arsenite (Ca–As–O) and sodium calcium arsenate hydrate (NaCaAsO₄·7.5H₂O) were present in the PC- and CKD-treated slurries as the key phases responsible for As(III) and As(V) immobilization, respectively. The XANES spectroscopy confirmed that the As(III) and As(V) oxidation states of the PC and CKD slurry samples were consistent with the speciated forms in the crystals identified by XRPD. EXAFS spectroscopy showed As–Ca bonding in the As(III)-PC and As(III)-CKD slurries. The main mechanism for the immobilization of As-contaminated soils with PC and CKD was strongly associated with the bonding between As(III) or As(V) and Ca.