A storm event-based approach to TMDL development

It is vitally important to define the critical condition for a receiving water body in the total maximum daily load (TMDL) development process. One of the major disadvantages of using a continuous simulation approach is that there is no guarantee that the most critical condition will be covered within the subjectively selected representative hydrologic period, which is usually several years depending on the availability of data. Another limitation of the continuous simulation approach, compared to a design storm approach, is the lack of an estimate of the risk involved. Because of the above limitations, a storm event-based critical flow-storm (CFS) approach was previously developed to explicitly address the critical condition as a combination of a prescribed stream flow and a storm event of certain magnitude, both having a certain frequency of occurrence and when combined, would create a critical condition. The CFS approach was tested successfully in a TMDL study for Muddy Creek in Virginia. The present paper reports results of a comparative study on the applicability of the CFS approach in Taiwan. The Dy-yu creek watershed in northern Taiwan differs significantly from Muddy Creek in terms of climate, hydrology, terrain, and other characteristics. Results show that the critical condition for different watersheds might be also different, and that the CFS approach could clearly define that critical condition and should be considered as an alternative method for TMDL development to a continuous simulation approach.     

Occurrence and distribution of polycyclic aromatic carbons in sludges from wastewater treatment plants in Guangdong, China

In this study, the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) were investigated in six sludge samples collected from Guangdong Province, China. Concentrations of PAHs varying from 2,534.1 to 6,926.6 μg kg^???1 (dry sludge) were observed in three municipal wastewater treatment plants with phenanthrene (Phe), fluoranthene, and pyrene being the main compounds. In addition, 682.6 μg kg^???1 PAHs were detected in one sludge sample from a food processing plant, with fluorene, Phe, and chrysene being the main components. No PAHs were detected in sludge samples obtained from two cosmetic plants. The levels and distributional characteristics of PAHs, polychlorinated biphenyls (PCBs), and polycyclic musks (PMs) from the samples were also compared. The results of this comparison indicated that petrochemical refineries and road traffic played important roles in the PAH loads in sludge, while PMs primarily originated from domestic wastewater and industrial wastewater from cosmetic plants. Finally, the presence of 98.8 μg kg^???1 PCBs in sludge suggested diffusional emission sources from electrical components containing PCBs.     

Effective removal of coordinated copper from wastewater using a new dithiocarbamate-type supramolecular heavy metal precipitant

A new dithiocarbamate-type heavy metal precipitant, sodium 1,3,5-hexahydrotriazinedithiocarbamate (HTDC), was prepared and used to remove coordinated copper from wastewater. In the reported dithiocarbamate-type precipitants, HTDC possesses the highest percentage of the effective functional groups. It could effectively precipitate copper to less than 0.5 mg l⁻¹ from both synthetic and actual industrial wastewater containing CuEDTA in the range of pH 3–9. UV–vis spectral investigation and elemental analysis suggested that the precipitate was a kind of coordination supramolecular compound, [Cu₃(HTDC)₂]_n. The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) indicated that the supramolecular precipitate was non-hazardous and stable in weak acid and alkaline conditions. Tests of an anion exchange resin D231 provided a clue to simultaneously remove excess HTDC and residual CuEDTA in practical process of wastewater treatment.     

A batch study on the bio-fixation of carbon dioxide in the absorbed solution from a chemical wet scrubber by hot spring and marine algae

Carbon dioxide mass transfer is a key factor in cultivating micro-algae except for the light limitation of photosynthesis. It is a novel idea to enhance mass transfer with the cyclic procedure of absorbing CO(2) with a high performance alkaline abosorber such as a packed tower and regenerating the alkaline solution with algal photosynthesis. Hence, the algae with high affinity for alkaline condition must be purified. In this study, a hot spring alga (HSA) was purified from an alkaline hot spring (pH 9.3, 62 degrees C) in Taiwan and grows well over pH 11.5 and 50 degrees C. For performance of HSA, CO(2) removal efficiencies in the packed tower increase about 5-fold in a suitable growth condition compared to that without adding any potassium hydroxide. But ammonia solution was not a good choice for this system with regard to carbon dioxide removal efficiency because of its toxicity on HSA. In addition, HSA also exhibits a high growth rate under the controlled pHs from 7 to 11. Besides, a well mass balance of carbon and nitrogen made sure that less other byproducts formed in the procedure of carboxylation. For analysis of some metals in HSA, such as Mg, Mn, Fe, Zn, related to the photosynthesis increased by a rising cultivated pH and revealed that those metals might be accumulated under alkaline conditions but the growth rate was still limited by the ratio of bicarbonate (useful carbon source) and carbonate. Meanwhile, Nannochlopsis oculta (NAO) was also tested under different additional carbon sources. The results revealed that solutions of sodium/potassium carbonate are better carbon sources than ammonia carbonate/bicarbonate for the growth of NAO. However, pH 9.6 of growth limitation based on sodium was lower than one of HSA. The integrated system is, therefore, more feasible to treat CO(2) in the flue gases using the algae with higher alkaline affinity such as HSA in small volume bioreactors.     

Comparison of organochlorine compound concentrations in colostrum and mature milk

Human breast milk represents the best choice for the nutrition of infants. It is often used for monitoring human exposures to environmental chemicals. Uniquely suited to meet human biological needs, breast milk composition, especially fat content, changes significantly with time from delivery. With the aim to compare the concentration of organochlorine compounds (OCs) in colostrum versus mature milk, we obtained samples of fourth-fifth day postpartum milk (colostrum) and day-14 postpartum milk (mature milk) from 12 women enrolled in the project "Early Childhood Development and PCB Exposure in Slovakia". The concentrations of selected organochlorine pesticides and congeners of polychlorinated biphenyls (PCBs) were measured using gas chromatography with electron capture detection and reported on lipid adjusted basis. No significant differences were found between organochlorine levels in colostrum and those in mature milk samples. A very close correlation was found between the concentrations of organochlorine compounds in colostrum and mature milk (Spearman correlation coefficient r=0.94-0.98 for PCBs, and r=0.85-0.99 for organochlorine pesticides, p<0.001 for all compounds). The present study concludes that the use of colostrum samples provides a close estimate of the child's exposure to OCs in the early neonatal period and demonstrates that, despite the lower fat content, colostrum specimens are adequate to conduct OC analyses.     

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol in supercritical water

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol (o-CP) in supercritical water (SCW) were studied in this paper under the conditions of 450 degrees C and 25 MPa. Experimental results indicated that the dechlorination of o-CP can be accelerated significantly by all alkalis investigated. The dechlorination of o-CP proceeded mainly via two pathways: hydrodechlorination and hydrolysis. Both of the two pathways can be promoted by alkalis, and the dechlorination of o-CP can be accelerated by both the cations and hydroxide ion dissociated from alkalis. The overall dechlorination of o-CP can be accelerated by cations via promoting the hydrodechlorination pathway, while, hydroxide ion via promoting the hydrolysis pathway. In addition, the hydrodechlorination can be accelerated faster by sodium alkalis than that by potassium ones, while, the hydrolysis can be promoted faster by potassium alkalis. This difference may be caused by the different charge density between potassium ion and sodium ion, and the different solubility and dissociation constant between potassium alkalis and sodium alkalis in SCW. Dechlorination of o-CP with addition of alkalis prior to supercritical water oxidation (SCWO) process not only can avoid the reactor corrosion caused by the generated hydrochloric acid in direct SCWO of o-CP, but also can reduce the formation of toxic chlorinated byproducts compared with direct SCWO process or SCWO of o-CP with addition of alkali.     

QSARs for the toxicity of polychlorinated dibenzofurans through DFT-calculated descriptors of polarizabilities, hyperpolarizabilities and hyper-order electric moments

DFT-B3LYP method with 6-31G(**) basis set was employed to fully optimize the electronic structures of 135 polychlorinated dibenzofurans and parent compound, namely dibenzofuran. It was demonstrated that polarizability anisotropy and mean polarizability could change sensitively and systematically with chlorine number and substitution pattern. And new quantitative structure-activity relationships (QSARs) focused on the binding affinities of aryl hydrocarbon receptor (AhR), aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) induction potencies of PCDFs were developed. It was concluded that polarizability anisotropy in conjunction with hyperpolarizabilties and hyper-order electric moments, e.g. octupole moments could well interpret the variation of toxicity of different congeners and dispersion interaction should be the leading form among various interactions. Although the terms of hyperpolarizabilities and hyper-order electric moments were not the same significant ones as polarizability anisotropy, the long-range interactions characterized by them should not be ignored in explaining the toxicity.     

Evaluation of nitrification inhibitor 3,4-dimethyl pyrazole phosphate on nitrogen leaching in undisturbed soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors (NI) as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, the efficacy of the new NI, 3,4-dimethyl pyrazole phosphate (DMPP), was tested under simulated high-risk leaching situations in two types of undisturbed soil columns. The results showed that the accumulative leaching losses of soil nitrate under treatment of urea with 1.0% DMPP, from columns of silt loam soil and heavy clay soil, were 66.8% and 69.5% lower than those soil columns tested with regular urea application within the 60 days observation, respectively. However, the losses of ammonium leaching were reversely increased 9.7% and 6.7% under the former treatment than the latter one. Application of regular urea with 1.0% DMPP addition can reduce about 59.3%-63.1% of total losses of inorganic nitrogen via leaching. The application of DMPP to urea had stimulated the inhibition effects of DMPP on the ammonium nitrification process in the soil up to 60 days. It is proposed that the DMPP could be used as an effective NI to control inorganic N leaching losses, minimizing the risk of nitrate pollution in shallow groundwater.     

Aerobic degradation of bisphenol A by Achromobacter xylosoxidans strain B-16 isolated from compost leachate of municipal solid waste

A novel bacterium designated strain B-16 was isolated from the compost leachate of the municipal solid waste (MSW) in a laboratory reactor. This strain was identified as a gram-negative bacterium, Achromobacter xylosoxidans that could grow on bisphenol A (BPA, a representative endocrine disruptor) as a sole carbon source under aerobic condition. BPA-degrading characteristics of strain B-16 were investigated in liquid cultures. The results show that BPA degradation was influenced by several factors (e.g. inoculum size, substrate concentration, temperature and pH, etc). The half-lives, optimum temperature and pH were found to be 0.58-3.1d, 35 degrees C and 7.0, respectively. BPA-degrading activity and cell growth were inhibited at high substrate concentration. Metabolic intermediates detected during the degradation process were identified as p-hydroxybenzaldehyde, p-hydroxybenzoic acid and p-hydroquinone, respectively. Metabolic pathway of BPA degradation was proposed in this study.     

Column studies on transport of deicing additive benzotriazole in a sandy aquifer and a zerovalent iron barrier

Benzotriazole (BTA), a chemical with wide industrial applications, is a typical additive in deicer/anti-icer used at airport. To achieve a better understanding of the transport behaviour and environmental fate of BTA, laboratory column studies have been performed on subsoil samples from Oslo Airport, Gardermoen. To explore possibilities for aquifer remediation, BTA behaviour was also studied in a column of granular zerovalent iron (Fe(0)). The subsoil column study demonstrates a very limited retardation of BTA. Consecutive loadings of BTA of the subsoil column showed no change of the break-through curve (BTC) and complete desorption was observed. The sorption behaviour of BTA to metallic iron (Fe(0)) was rather complex. Considerable retardation was observed in the Fe(0) column and repeated BTA loading resulted in an earlier break-through. Between 20% and 50% of the input concentration was retained permanently in the iron (Fe(0)) column. The BTA sorption to metallic iron was found to be enhanced by chloride which lowered the break-through concentration (i.e the C/C(0) plateau). The fraction of BTA remaining in the iron column was found to vary with the flow rate, indicating a time dependant multilayer sorption mechanism. The steady increase in the amount of adsorbed BTA to the iron column during loading corresponds to a rather strong bonding of 4-15 BTA layers to the iron surface. A very slow desorption of BTA was observed; even after flushing with 753 pore volumes of BTA free water, 7.5% of the BTA remained in the column. A geochemical model was developed based on PHREEQC-2 to simulate the sorption and transport of BTA in the tested materials. The BTA sorption was modelled with Freundlich sorption isotherms, as earlier determined in batch experiments. A slight adjustment of the Freundlich parameters was required to fit the observed column break-through. However, our model was not able to simulate the long-term retainment of BTA in the granular iron columns. The simulations confirm the high mobility of BTA in groundwater aquifers and suggest that zerovalent iron could be used to retain a BTA plume, although oxidation of the sorbent might reduce the long-term performance of such a remediation scheme and slow desorption has been observed.