Ozonation of oxytetracycline and toxicological assessment of its oxidation by-products

Antibiotic formulation effluents are well known for their difficult elimination by traditional bio-treatment methods and their important contribution to environmental pollution due to its fluctuating and recalcitrant nature. In the present study the effect of ozonation on the degradation of oxytetracycline (OTC) aqueous solution (100mgl(-1)) at different pH values (3, 7 and 11) was investigated. Ozone (11mgl(-1) corresponds the concentration of ozone in gas phase) was chosen considering its rapid reaction and decomposition rate. The concentration of oxytetracycline, chemical oxygen demand (COD), biochemical oxygen demand (BOD) and BOD5/COD ratio were the parameters to evaluate the efficiency of the ozonation process. In addition, the toxic potential of the OTC degradation was investigated by the bioluminescence test using the LUMIStox 300 instrument and results were expressed as the percentage inhibition of the luminescence of the marine bacteria Vibrio fischeri. The results demonstrate that ozonation as a partial step of a combined treatment concept is a potential technique for biodegradability enhancement of effluents from pharmaceutical industries containing high concentration of oxytetracycline provided that the appropriate ozonation period is selected. At pH 11 and after 60min of ozonation of oxytetracycline aqueous solutions (100 and 200mgl(-1)) the BOD5/COD ratios were 0.69 and 0.52, respectively. It was also shown that COD removal rates increase with increasing pH as a consequence of enhanced ozone decomposition rates at elevated pH values. The results of bioluminescence data indicate that first by-products after partial ozonation (5-30min) of OTC were more toxic than the parent compound.     

Single-well, gas-sparging tests for evaluating the in situ aerobic cometabolism of cis-1,2-dichloroethene and trichloroethene

This study developed single-well, gas-sparging tests for assessing the feasibility of in situ aerobic cometabolism of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE) using propane and methane as growth substrates. Tests were performed in groundwater contaminated with TCE (100-400 microg l(-1)) and cis-DCE (20-60 microg l(-1)). A series of gas-sparging tests was performed by first sparging ("bubbling") gas mixtures in a well fitted with a "straddle" packer and then periodically sampling groundwater from the same well to develop concentration profiles and to estimate transformation rate coefficients. Evidence that gas-sparging of propane (or methane) and oxygen had stimulated organisms expressing a propane (or methane) monooxygenase enzyme system and the capability to transform TCE and cis-DCE included: (1) the transformation of sparged ethylene and propylene to their corresponding cometabolic by-products, ethylene oxide and propylene oxide, (2) the transformation of both cis-DCE and TCE in the propane-sparged well, (3) the transformation of cis-DCE in the methane-sparged well, and (4) the inhibition of ethylene and propylene transformations in the presence of acetylene, a known monooxygenase inactivator. At a well sparged with propane, first-order rate coefficients for propane utilization and ethylene and propylene transformation were similar, ranging from 0.007 to 0.010 h(-1). At the well sparged with methane, the propylene first-order transformation rate coefficient was 0.028 h(-1), a factor of 1.8 and 1.6 greater than methane and ethylene, respectively. The results demonstrated that gas-sparging tests are a rapid, low-cost means of assessing the potential for the in situ aerobic cometabolism of cis-DCE and TCE.     

Response of microbial growth to orthophosphate and organic carbon influx in copper and plastic based plumbing water systems

Consequences of orthophosphate addition for corrosion control in water distribution pipes with respect to microbial growth were investigated using batch and dynamic tests. Batch tests showed that the release of copper in either low or high organic carbon content water was decreased by 69% and 56% with addition 206 microg PO(4)-P, respectively. Dosing of orthophosphate against corrosion did not increase microbial growth potential in the water and in the biofilm in both corroded and uncorroded systems receiving tap water with a low content of organic carbon and of biodegradable organic fraction. However, in tap water having a high concentration of organic carbon from acetate addition, orthophosphate addition promoted the growth of bacteria, allowed more bacteria to assemble on corroded and uncorroded surfaces, and increased the consumption of organic carbon. Orthophosphate consumption did not exceed 1% of the amount of easily biodegradable organic carbon required for microbial growth, and the orthophosphate demand for corrosion control greatly exceeded the nutritional requirement of microbial growth. The results of the dynamic tests demonstrated that there was a significant effect of interaction between biodegradable organic carbon and orthophosphate on biofilm growth, whereby the effect of orthophosphate flux on microbial growth was dependent on the levels of biodegradable organic carbon. Controlling an easily biodegradable organic carbon would be therefore necessary to minimize the microbial growth potential induced by orthophosphate-based anticorrosion treatment.     

Hydrochemistry of urban groundwater, Seoul, Korea: the impact of subway tunnels on groundwater quality

Hydrogeologic and hydrochemical data for subway tunnel seepage waters in Seoul (Republic of Korea) were examined to understand the effect of underground tunnels on the degradation of urban groundwater. A very large quantity of groundwater (up to 63 million m³ year^− 1) is discharged into subway tunnels with a total length of 287 km, resulting in a significant drop of the local groundwater table and the abandonment of groundwater wells. For the tunnel seepage water samples (n = 72) collected from 43 subway stations, at least one parameter among pathogenic microbes (total coliform, heterotrophic bacteria), dissolved Mn and Fe, NH₄⁺, NO₃⁻, turbidity, and color exceeded the Korean Drinking Water Standards. Locally, tunnel seepage water was enriched in dissolved Mn (avg. 0.70 mg L^− 1, max. 5.58 mg L^− 1), in addition to dissolved Fe, NH₄⁺, and pathogenic microbes, likely due to significant inflow of sewage water from broken or leaking sewer pipes.Geochemical modeling of redox reactions was conducted to simulate the characteristic hydrochemistry of subway tunnel seepage. The results show that variations in the reducing conditions occur in urban groundwater, dependent upon the amount of organic matter-rich municipal sewage contaminating the aquifer. The organic matter facilitates the reduction and dissolution of Mn- and Fe-bearing solids in aquifers and/or tunnel construction materials, resulting in the successive increase of dissolved Mn and Fe. The present study clearly demonstrates that locally significant deterioration of urban groundwater is caused by a series of interlinked hydrogeologic and hydrochemical changes induced by underground tunnels.     

Feasibility of using microalgal biomass cultured in domestic wastewater for the removal of chromium pollutants

The feasibility of obtaining and using the biomass of a microalga, Chlorella miniata, from domestic wastewater (DW) cultures for the removal of chromium(III) [Cr(III)] and chromium(VI) [Cr(VI)] was compared with that from commercial Bristol medium (BM). Results showed that Chlorella miniata cultured in DW under 16-8 hours light-dark cycle [DW(16-8)] had similar growth to that in BM [BM(16-8)], but these two biomass had different biochemical compositions, and the former one had lower carbohydrate and higher protein content. When cultured in domestic wastewater, a higher biomass was obtained under continuous illumination [DW(24-0)], and the cells had higher carbohydrate and lower protein concentrations than that of DW(16-8). The spectra of the Fourier transform infrared spectrometer revealed that the functional groups on the surface of the three kinds of biomass--DW(16-8), DW(24-0), and BM(16-8)--were comparable, except an additional peak at 1731 cm(-1) was found in the biomass cultured in domestic wastewater, which was probably the result of bacterial contamination. Although biochemical differences were found among the three kinds of microalgal biomass, similar biosorption performances to chromium pollutants were recorded, with approximately 75% Cr(III) and 100% Cr(VI) removed at equilibrium in Cr(III) and Cr(VI) experiments, respectively, when dead biomass was used as a biosorbent. Therefore, it is possible to culture Chlorella miniata in domestic wastewater and use the biomass for the removal of chromium pollutants.     

Real-world in-use activity, fuel use, and emissions for nonroad construction vehicles: a case study for excavators

A study design was developed and demonstrated for deployment of a portable emission measurement system (PEMS) for excavators. Excavators are among the most commonly used vehicles in construction activities. The PEMS measured nitric oxide, carbon monoxide, hydrocarbons, carbon dioxide, and opacity-based particulate matter. Data collection, screening, processing, and analysis protocols were developed to assure data quality and to quantify variability in vehicle fuel consumption and emissions rates. The development of data collection procedures was based on securing the PEMS while avoiding disruption to normal vehicle operations. As a result of quality assurance, approximately 90% of the attempted measurements resulted in valid data. On the basis of field data collected for three excavators, an average of 50% of the total nitric oxide emissions was associated with 29% of the time of operation, during which the average engine speed and manifold absolute pressure were significantly higher than corresponding averages for all data. Mass per time emission rates during non-idle modes (i.e., moving and using bucket) were on average 7 times greater than for the idle mode. Differences in normalized average rates were influenced more by intercycle differences than intervehicle differences. This study demonstrates the importance of accounting for intercycle variability in real-world in-use emissions to develop more accurate emission inventories. The data collection and analysis methodology demonstrated here is recommended for application to more vehicles to better characterize real-world vehicle activity, fuel use, and emissions for nonroad construction equipment.     

Characterization of ambient fine particles in the northwestern area and Anchorage, Alaska

Ambient PM2.5 (particulate matter less than 2.5 microm in aerodynamic diameter) in the northwestern United States and Alaska is dominated by carbonaceous compounds associated with wood burning and transportation sources. PM2.5 source characterization studies analyzing recent PM2.5 speciation data have not been previously reported for these areas. In this study, ambient PM2.5 speciation samples collected at two monitoring sites located in the northwestern area, Olympic Peninsula, WA, and Portland, OR, and one monitoring site located in Anchorage, AK, were characterized through source apportionments. Gasoline vehicle, secondary sulfate, and wood smoke were the largest sources of PM2.5 collected at the Anchorage, Olympic, and Portland monitoring sites, respectively. Secondary sulfates showed an April peak at Anchorage and a November peak at Portland that are likely related to the increased photochemical reaction and long-range transport in Anchorage and meteorological stagnation in Portland. Secondary nitrate at the Olympic site showed a weak summer high peak that could be caused by seasonal tourism in the national park. Backward trajectories suggested that the elevated aged sea salt concentrations at the Portland monitoring site could be regional transport of sea salt that passed through other contaminated air sheds along the coast. Oil combustion emissions that might originate from ships and ferries were observed at the Olympic monitoring site.     

Characterization of real-world activity, fuel use, and emissions for selected motor graders fueled with petroleum diesel and B20 biodiesel

Motor graders are a common type of nonroad vehicle used in many road construction and maintenance applications. In-use activity, fuel use, and emissions were measured for six selected motor graders using a portable emission measurement system. Each motor grader was tested with petroleum diesel and B20 biodiesel. Duty cycles were quantified in terms of the empirical cumulative distribution function of manifold absolute pressure (MAP), which is an indicator of engine load. The motor graders were operated under normal duty cycles for road maintenance and repair at various locations in Wake and Nash Counties in North Carolina. Approximately 3 hr of quality-assured, second-by-second data were obtained during each test. An empirical modal-based model of vehicle fuel use and emissions was developed, based on stratifying the data with respect to ranges of normalized MAP, to enable comparisons between duty cycles, motor graders, and fuels. Time-based emission factors were found to increase monotonically with MAP. Fuel-based emission factors were mainly sensitive to differences between idle and non-idle engine operation. Cycle average emission factors were estimated for road "resurfacing," "roading," and "shouldering" activities. On average, the use of B20 instead of petroleum diesel leads to a negligible decrease of 1.6% in nitric oxide emission rate, and decreases of 19-22% in emission rates of carbon monoxide, hydrocarbons, and particulate matter. Emission rates decrease significantly when comparing newer engine tier vehicles to older ones. Significant reductions in tailpipe emissions accrue especially from the use of B20 and adoption of newer vehicles.     

Effects of oyster shell on soil chemical and biological properties and cabbage productivity as a liming materials

Oyster shell, a byproduct of shellfish-farming in Korea and containing a high amount of CaCO(3), has a high potential to be used as a liming material in agriculture. However, the agricultural utilization of oyster shell is limited due to its high concentration NaCl. The oyster-shell meal collected had a low concentration of water soluble NaCl (mean 2.7 g kg(-1)), which might be a result of stacking the material for 6 months in the open field. It has a very similar liming potential with calcium carbonate, with 3.4 and 3.8 Mg ha(-1) for silt loam (SiL, pH 6.2) and sandy loam (SL, pH 5.8) to bring the soil pH to 6.5, respectively. To determine the effect of crushed oyster-shell meal on improving soil chemical and biological properties and crop plant productivity, oyster-shell meal was applied at rates of 0, 4, 8, 12, and 16 Mg ha(-1) before transplanting Chinese cabbage (Brassica campestris L.) in the two soils mentioned above. Soil pH was significantly increased to 6.9 and 7.4 by 16 Mg ha(-1) shell meal application (4 times higher level than the recommendation) in SiL and SL, respectively, at harvesting stage. The effect of liming was found higher in SL compared to SiL soil, probably due to the different buffering capacity of the two soils. The concentration of NaCl and EC value of soils were found slightly increased with shell meal applications, but no salt damage was observed. Oyster-shell meal application increased soil organic matter, available P, and exchangeable cations concentrations. The improved soil pH and nutrient status significantly increased the microbial biomass C and N concentrations and stimulated soil enzyme activities. With the exception of acid phosphomonoesterase (PMEase) activity, which decreased with increasing soil pH in SL but slightly increased in SiL, the activities of urease and alkali PMEase increased markedly with increasing soil pH by shell meal application. The improved soil chemical and biological properties resulted in increased crop productivity. The highest yield in Chinese cabbage was achieved following the application of 8 Mg ha(-1) oyster-shell meal. Conclusively, crushed oyster shell could be used as an alternative liming material to restore the soil chemical and microbial properties in upland soil and to increase crop productivity.     

Preparation of Alginic Acid and Metal Alginate from Algae and their Comparative Study

Alginic acid and metal alginates are prepared from fresh algae using extraction method. A FTIR spectrum indicates that alginic acid is converted into the metal alginate. Comparing calcium and cobalt alginates, asymmetric stretching of free carboxyl group of calcium alginate at 1630 cm⁻¹ is shifted to 1585 cm⁻¹ in cobalt alginate, due to the change of charge density, radius and atomic weight of the cation, creating a new environment around the carbonyl group. The strong exothermic peak of alginic acid in DSC thermogram indicates the decomposition of biopolymer, whereas strong exothermic peak of metal alginate in DSC thermogram attributed to the decomposition of biopolymer and formation of respective carbonate. Based on DSC study, the decomposition of cobalt alginate occurs at higher temperature comparing to those of sodium and calcium alginate, which may conclude into the higher stability of cobalt alginate. TGA results reveal that, cobalt alginate is more stable than calcium and sodium alginate at 300 °C temperature. Surface morphology (at same magnification), as well as porosity (%) and pore size distribution results change with metals present in different metal alginates.