N-亚硝基二甲胺及其前体物在污水处理厂中去除的研究进展

N-亚硝基二甲胺(NDMA)是近年来发现的水或废水氯消毒的副产物,被美国环境保护署认定为可疑致癌化合物.介绍了NDMA的形成机制及其与NDMA前体物的来源.综述了NDMA及其前体物在污水处理厂中的去除现状和去除技术.在此基础上,展望了NDMA及其前体物的未来研究方向,提出了开展国内NDMA研究工作的必要性.     

Effects of photodegradation of dissolved organic matter on the binding of benzo(a)pyrene

Dissolved organic matter (DOM) in natural waters can bind various organic pollutants, and the affinity of this binding is strongly influenced by the chemical characteristics of the DOM and water pH. This study examined the effects of photochemically induced alteration of the DOM's chemical properties and water pH on the binding of benzo(a)pyrene (BaP). Time- and pH-series of solar-simulated irradiations were performed on a natural water sample and aqueous DOM solutions prepared from aquatic and soil humic substances. The binding affinity of BaP, expressed as a partition coefficient of a compound to DOM, decreased substantially after the DOM samples were irradiated over environmentally relevant radiation doses and pH ranges. The lowering of the pH due to the photoproduction of acidic products often partly offsets the reduction of the binding affinity caused by direct photoalteration of the DOM's chemical structure. The decrease of the binding affinity, after correction for the photoinduced pH change, was positively correlated with the decrease in the molecular weight and the aromaticity of the DOM in the course of irradiation. Increasing O(2) abundance accelerated the decrease of the binding affinity as a result of enhanced DOM photodegradation. Visible light played a more important role in reducing the molecular weight and aromaticity of the DOM than in reducing the content of dissolved organic carbon (DOC) via photoremineralization while the reverse was true for UV radiation, indicating that photochemical reduction of the binding affinity may occur in natural waters at depths greater than UV radiation can reach. A decrease of the affinity of DOM for binding BaP will increase the free dissolved fraction of BaP and thus its availability and toxicity to aquatic organisms. The results from this study may have similar implications for organic pollutants other than BaP.     

A method of assessing air toxics concentrations in urban areas using mobile platform measurements

The objective of this paper is to demonstrate an approach to characterize the spatial variability in ambient air concentrations using mobile platform measurements. This approach may be useful for air toxics assessments in Environmental Justice applications, epidemiological studies, and environmental health risk assessments. In this study, we developed and applied a method to characterize air toxics concentrations in urban areas using results of the recently conducted field study in Wilmington, DE. Mobile measurements were collected over a 4- x 4-km area of downtown Wilmington for three components: formaldehyde (representative of volatile organic compounds and also photochemically reactive pollutants), aerosol size distribution (representing fine particulate matter), and water-soluble hexavalent chromium (representative of toxic metals). These measurements were,used to construct spatial and temporal distributions of air toxics in the area that show a very strong temporal variability, both diurnally and seasonally. An analysis of spatial variability indicates that all pollutants varied significantly by location, which suggests potential impact of local sources. From the comparison with measurements at the central monitoring site, we conclude that formaldehyde and fine particulates show a positive correlation with temperature, which could also be the reason that photochemically generated formaldehyde and fine particulates over the study area correlate well with the fine particulate matter measured at the central site.     

Impact of downward-mixing ozone on surface ozone accumulation in southern Taiwan

The ozone that initially presents in the previous day's afternoon mixing layer can remain in the nighttime atmosphere and then be carried over to the next morning. Finally, this ozone can be brought to the ground by downward mixing as mixing depth increases during the daytime, thereby increasing surface ozone concentrations. Variation of ozone concentration during each of these periods is investigated in this work. First, ozone concentrations existing in the daily early morning atmosphere at the altitude range of the daily maximum mixing depth (residual ozone concentrations) were measured using tethered ozonesondes on 52 experimental days during 2004-2005 in southern Taiwan. Daily downward-mixing ozone concentrations were calculated by a box model coupling the measured daily residual ozone concentrations and daily mixing depth variations. The ozone concentrations upwind in the previous day's afternoon mixing layer were estimated by the combination of back air trajectory analysis and known previous day's surface ozone distributions. Additionally, the relationship between daily downward-mixing ozone concentration and daily photochemically produced ozone concentration was examined. The latter was calculated by removing the former from daily surface maximum ozone concentration. The measured daily residual ozone concentrations distributed at 12-74 parts per billion (ppb) with an average of 42 +/- 17 ppb are well correlated with the previous upwind ozone concentration (R2 = 0.54-0.65). Approximately 60% of the previous upwind ozone was estimated to be carried over to the next morning and became the observed residual ozone. The daily downward-mixing ozone contributes 48 +/- 18% of the daily surface maximum ozone concentration, indicating that the downward-mixing ozone is as important as daily photochemically produced ozone to daily surface maximum ozone accumulation. The daily downward-mixing ozone is poorly correlated with the daily photochemically produced ozone and contributes significantly to the daily variation of surface maximum ozone concentrations (R2 = 0.19). However, the contribution of downward-mixing ozone to daily ozone variation is not included in most existing statistical models developed for predicting daily ozone variation. Finally, daily surface maximum ozone concentration is positively correlated with daily afternoon mixing depth, attributable to the downward-mixing ozone.     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

The relationship of the monoterpene composition in the atmosphere,the foliar emission gas and the leaf oil of Pinus densiflora

Monoterpene compositions in the atmosphre in a pine forest, the foliar emission gas and the leaf oil of pine needles were compared. The emission rate of each monoterpene from pine needles was proportional to the product of the amount in the leaf oil and the approximate vapor pressure. The composition of monoterpenes in the atmosphere is rather well explained by considering foliar emission rates with the supposition that the terpenes emitted into the atmosphere react with ozone and photochemically with nitrogen oxides.     

Sources and fate of nitrosodimethylamine and its precursors in municipal wastewater treatment plants.

To assess the occurrence and fate of nitrosodimethylamine (NDMA) and its precursors in wastewater treatment plants, samples from wastewater treatment plants and industrial sources were analyzed for NDMA, total NDMA precursors, and dimethylamine (DMA). The median concentration of NDMA in untreated wastewater was approximately 80 ng/L, with maximum concentrations up to 790 ng/L presumably occuring because of sources unrelated to domestic wastewater. Concentrations of DMA in untreated wastewater ranged from approximately 50 to 120 microg/L and accounted for a majority of the NDMA precursors. The removal of NDMA during secondary biological treatment exhibited considerable variability, with overall removal ranging from 0 to 75%. In contrast, removal of NDMA precursors and DMA generally exceeded 70%. The median concentration of NDMA in secondary effluent before disinfection was 46 ng/L. Although DMA was removed during secondary treatment, other NDMA precursors in wastewater effluent will result in formation of additional NDMA upon disinfection with chloramines.     

Kinetics of oxidation of methylhydrazines in water. Factors controlling the formation of 1,1-dimethylnitrosamine

The kinetics of oxidation of methylhydrazine ($\text{MMH}$) and 1,1-dimethylhydrazine ($\text{UDMH}$) by dissolved oxygen in water has been measured at various acidities as a function of catalyst (cupric ion) concentration. In dilute solutions the oxidation occurs through a cupric ion catalyzed process as well as by an uncatalyzed step. The extent of formation of nitrosodimethylamine ($\text{NDMA}$) depends upon the initial $\text{UDMH}$ concentration. In dilute solutions $\text{NDMA}$ is not formed, but in more concentrated solutions, $\text{NDMA}$ formation increases with increasing $\text{UDMH}$ content, reaches a maximum at 60–80% $\text{UDMH}$ (by volume) and then decreases. The $\text{NDMA}$ yield appears to approximately parallel the viscosity of the medium, and it is speculated that the factors which control viscosity may also be responsible for governing $\text{NDMA}$ formation.     

Photochemical reduction of hexavalent chromium in glycerol-containing solutions

Hexavalent chromium [Cr(VI)] in the form of potassium dichromate was photochemically reduced to trivalent chromium [Cr(III)] in aqueous solutions containing glycerol. This reaction occurred rapidly during irradiation with either unfiltered sunlight or a UVA-emitting light source. Photochemical reduction of Cr(VI) was pH-dependent and did not occur in dilute solutions of sodium hydroxide. In acidified solutions, the reduction occurred at elevated rates and at lower concentrations of glycerol. This reaction was found to be dependent on the unsubstituted alcohol groups of glycerol since alpha-phosphoglycerol and beta-phosphoglycerol did not support the photochemical reduction of Cr(VI). These findings suggest that glycerol or related polyols can be used for the remediation of hexavalent (toxic) chromium at contaminated environmental sites.     

Photochemically induced interactions in Ekofisk crude oil

Evidence for photochemically induced interactions in Ekofisk crude oil as a thin film on top of a water surface has been obtained by isotopic labelling experiments and field desorbtion mass spectrometry. The interaction behaviour to the high molecular weight resin/asphaltene material has been discussed by invoking the concept of molecular assemblies like micelles and vesicles. This latter chromophoric material has also been shown to have an appreciable sensitizing effect, resulting in a substantial transformation of carbon 14 radiolabelled species, including straight chain n-alkanes.Isotopic studies do not provide evidence for interactions in Ekofisk crude oil constituents kept in darkness, where only a very slow transformation/degradation of oil components has been observed.The implication of these findings has been discussed.     

Chloroform in the environment: occurrence,sources, sinks and effects

The chloroform flux through the environment is apparently constant at some 660±220 Gg yr⁻¹ (±1σ) and about 90% of the emissions are natural in origin: the largest single source being in offshore sea water (contributing 360±90 Gg yr⁻¹), with soil processes the next most important (220±100 Gg yr⁻¹). Other natural sources, mainly volcanic and geological, account for less than 20 Gg yr⁻¹. The non-natural sources total 66±23 Gg yr⁻¹ and are much better characterised than the natural sources. They are predominantly the result of using strong oxidising agent on organic material in the presence of chloride ion, a direct parallel with the natural processes occurring in soils.

Chloroform partitions preferentially into the atmosphere; the equilibrium distribution is greater than 99% and the average global atmospheric concentration has been calculated to be 18.5 pmol mol⁻¹. Atmospheric oxidation, the principal removal process, is approximately in balance with the identified source fluxes. Chloroform is widely dispersed in the aquatic environment (even naturally present in some mineral waters). Consequently, it is also widely dispersed in the tissue of living creatures and in foodstuffs but there is little evidence of bioaccumulation and the quantities in foodstuffs and drinking water are not problematical for human ingestion at the highest concentrations found. Definitive studies have shown that current environmental concentrations of chloroform do not present an ecotoxicological risk, even to fish at the embryonic and larval stages when they are most susceptible.

By virtue of the very small amounts that actually become transported to the stratosphere, chloroform does not deplete ozone materially, nor is it a photochemically active volatile organic compound (VOC). It has a global warming potential that is less than that of the photochemically active VOCs and is not classed as a greenhouse gas.     

Identification of oxidized TNT metabolites in soil samples of a former ammunition plant

Water extracts of soil samples of the former ammunition plant “Tanne” near Clausthal-Zellerfeld, Lower Saxony, Germany, were investigated for highly polar oxidized 2,4,6-trinitrotoluene (TNT) metabolites. 0.4 to 9.0 mg/kg dry soil 2,4,6-trinitrobenzoic acid (TNBA) and 5.8 to 544 mg/kg dry soil 2-amino-4,6-dinitrobenzoic acid (2-ADNBA) were found. In addition to the oxidized metabolites, TNT, 4- and 2-aminodinitrotoluene (4- and 2-ADNT), and 2,4-dinitrotoluene (2,4-DNT) were extractable with water. Most interestingly, in one sample, 2-ADNBA represented the main contaminant. The origin of the oxidized nitroaromatics is unknown at this time. They might be generated chemically or photochemically. Furthermore, a biological synthesis seems possible.     

Computer estimation of the Atmospheric gas-phase reaction rate of organic compounds with hydroxyl radicals and ozone

The Atmospheric Oxidation Program (AOP) is a computer program that estimates the rate constant for the atmospheric, gas-phase reaction between photochemically produced hydroxyl radicals (OH) and organic chemicals. It also estimates the rate constant for the gas-phase reaction between ozone and olefinic/acetylenic compounds. AOP, which uses estimation methods developed by Atkinson and co-workers, estimates more accurate rate constants than the PCFAP (Fate of Atmospheric Pollutants) program that was part of the U.S. EPA's Graphical Exposure Modeling System (GEMS). Due to its superior predictive ability, the EPA is currently using AOP to evaluate the atmospheric fate of compounds defined under Sections 4, 5 and 6 of the Toxic Substances Control Act (TSCA).     

Toxicity of pH,heavy metals and bisulfite to a freshwater green alga

Low pH markedly reduced the growth and photosynthetic activity of an $\text{Ankistrodesmus}$ sp. The alga could not grow at pH 3 and only slight growth occurred at pH 4. The alga grew well above pH 4 with maximum growth occurring at pH 6. The fixation of ¹⁴CO₂ followed a similar pattern with pH. The algal cells were also sensitive to mercury and bisulfite in acidic conditions. Algal growth and photosynthesis were reduced by mercury and bisulfite more at pH 5 than at pH 7. Lead was relatively non-toxic to the algal cells at both pH levels. Bisulfite inhibited the membrane transport of α-amino-¹⁴C-isobutyric acid at pH 5 but not at pH 7. The results suggest that algal growth and activity may be reduced in acidic lakes by low pH and that the toxicity of mercury and bisulfite is enhanced in acidic conditions.     

A high performance liquid chromatography method for determination of gas-phase hydrogen peroxide in ambient air using Fenton's chemistry

A new method for determination of hydrogen peroxide in atmospheric samples is described. Cryogenically collected H2O2 is reacted with sodium salicylate in the presence of Fe(2+) to produce dihydroxybenzoate, which is separated from the reaction mixture by high performance liquid chromatography and detected by UV absorption. Measurements of atmospheric H2O2 were conducted in Las Vegas, NV from June 1999 to December 1999 to evaluate and characterize the method. Measured mixing ratios of H2O2 (there were also non-detects) ranged from 0.012 to 2.74 ppbv, with expected correlations to primary gaseous pollutants and strong seasonal variation consistent with a photochemically derived species. It was concluded that the method is easy to use and has sufficient sensitivity and selectivity to be useful in atmospheric monitoring.     

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.     

Effect of initial pH control on biological phosphorus removal induced by the aerobic/extended-idle regime

Recently, it has been reported that biological phosphorus removal (BPR) can be induced by an aerobic/extended-idle (AEI) regime. This study further investigated the effect of initial pH ranging from 6.6 to 8.2 on BPR in the AEI process, and compared the BPR performance between the AEI and the anaerobic/oxic (A/O) regimes under their optimal initial pH value. Experimental results firstly showed that phosphorus removal linearly increased with initial pH increasing from 6.6 to 7.8, but slightly decreased when initial pH increased from 7.8 to 8.2. The optimal initial pH should be controlled at 7.8, and the phosphorus removal at initial pH 7.8 was approximately 1.7-time than that at initial pH 6.6. The mechanism studies showed that the biomass cultured at initial pH 7.8 contained more polyphosphate accumulating organisms (PAOs), lower glycogen accumulating organisms (GAOs), and had higher activities of exopolyphosphatase and polyphosphate kinase than that cultured at initial pH 6.6. Cyclic studies revealed that initial pH control affected the transformations of intracellular polyhydroxyalkanoates and glycogen, which might thereby influence microbial competition between PAOs and GAOs. Then, BPR performance between the AEI and the A/O regimes by adjusting initial pH at 7.8 was also compared. The results showed the AEI regime could drive a better BPR than the generally accepted A/O regime (98% vs 88%). Finally, controlling initial pH at 7.8 to promote BPR in the AEI process was confirmed for a municipal wastewater.     

Roadside particle number distributions and relationships between number concentrations, meteorology, and traffic along a northern California freeway

Particle number distributions were measured simultaneously upwind and downwind of a suburban-agricultural freeway to determine relationships with traffic and meteorological parameters. Average traffic volumes were 6330 vehicles/hr with 10% heavy-duty vehicles, and volumes were higher in July than November. Most downwind particle number distributions were bimodal, with a primary mode at approximately 10-25 nm, indicating that newly formed particles were sampled. Total downwind 6-237 nm particle number concentrations (Ntot) ranged from 9.3 x 10(3) to 2.5 x 10(5) cm(-3), with higher daily average concentrations in November compared with July. Ntot correlated with wind speed, temperature, and relative humidity. Upwind photochemically initiated nucleation likely led to elevated background nanoparticle concentrations in July, as evidenced by increasing upwind distribution modal diameter with increasing temperature and a strong correlation between upwind Ntot and solar radiation. Also in summer, Ntot showed stronger correlation with heavy-duty vehicle volumes than wind speed, temperature, and relative humidity. These results indicate the importance of measuring background particle size distributions simultaneously with roadside distributions. There may be a minimum vehicle volume from which useful real-world vehicle particle number distributions can be measured at roadside, even when collecting samples within 10 m of the traveled lanes.     

Influence of pH on pesticide sorption by soil containing wheat residue-derived char

Field burning of crop residues incorporates resulting chars into soil and may thus influence the environmental fate of pesticides in the soil. This study evaluated the influence of pH on the sorption of diuron, bromoxynil, and ametryne by a soil in the presence and absence of a wheat residue-derived char. The sorption was measured at pHs approximately 3.0 and approximately 7.0. Wheat char was found to be a highly effective sorbent for the pesticides, and its presence (1% by weight) in soil contributed >70% to the pesticide sorption (with one exception). The sorption of diuron was not influenced by pH, due to its electroneutrality. Bromoxynil becomes dissociated at high pHs to form anionic species. Its sorption by soil and wheat char was lower at pH approximately 7.0 than at pH approximately 3.0, probably due to reduced partition of the anionic species of bromoxynil into soil organic matter and its weak interaction with the carbon surface of the char. Ametryne in its molecular form at pH approximately 7.0 was sorbed by char-amended soil via partitioning into soil organic matter and interaction with the carbon surface of the char. Protonated ametryne at pH approximately 3.0 was substantially sorbed by soil primarily via electrostatic forces. Sorption of protonated ametryne by wheat char was also significant, likely due not only to the interaction with the carbon surface but also to interactions with hydrated silica and surface functional groups of the char. Sorption of ametryne by char-amended soil at pH approximately 3.0 was thus influenced by both the soil and the char. Environmental conditions may thus significantly influence the sorption and behavior of pesticides in agricultural soils containing crop residue-derived chars.     

Effects of subacute doses of cadmium on pH-stressed Leptophlebia marginata (L.) and Baetis rhodani Pictet (Insecta: Ephemeroptera)

Cd uptake, emergence, survival and locomotory activity at two pH levels were studied in a 27-day experiment with Leptophlebia marginata and in a 19-day experiment with Baetis rhodani. Model ecosystems containing recirculating stream water, patches of sediment and leaves, simulated a natural stream. During the experiments, concentrations of Al, Cd, Fe and Zn increased in the water at pH 5, while conductivity decreased. Cd was taken up by both species at a rate which indicated linear uptake kinetics. No steady state of Cd in the animals was observed. The larvae of B. rhodani contained significantly more Cd than the adults (p<0.001). Uptake of Cd by Baetis rhodani was higher at pH 7 than at pH 5 (p<0.05). The survivial of L. marginata was not influenced by pH and Cd stress, but emergence was significantly reduced (p<0.05). The survival and the emergence of B. rhodani were reduced by low pH and also by Cd addition (p<0.01). At pH 7, Cd had no significant adverse effect on survival. Locomotory activity of Baetis rhodani was reduced by low pH and additionally by Cd stress.