Nonylphenol ethoxylates and other additives in aircraft deicers, antiicers, and waters receiving airport runoff

Samples of nine different formulations of aircraft deicer and antiicer fluids (ADAF) were screened for the presence of selected surfactants. Nonylphenol ethoxylates (NPnEO) were identified in three ADAF formulations, octylphenol ethoxylates were identified in two formulations, and six formulations contained alcohol ethoxylates. A preliminary field study was conducted at General Mitchell International Airport, Milwaukee, WI, to quantify NPnEO (n = 1-15) and one of its byproducts, nonylphenol (NP), in airport runoff. Samples were collected from two airport outfalls, from the receiving stream, and from an upstream reference site during intensive ADAF application events. NPnEO was measured at concentrations up to 1190microg/L in airport outfall samples, up to 77 ug/L in samples from the receiving stream and less than 5.0 microg/L from the upstream reference. Concentrations of glycol and other ADAF-related constituents, including NPnEO, were reduced by approximately 1 order of magnitude between the outfall sites and the receiving stream site; however, concentrations of NP in the receiving stream remained similar to those from the outfalls (< 0.04 microg/L at the upstream reference, 0.98 and 7.67 microg/L at outfalls, and 3.89 microg/L in the receiving stream). The field data suggest that NP is generated through degradation of NPnEO from airport runoff.     

Aquatic toxicity of nine aircraft deicer and anti-icer formulations and relative toxicity of additive package ingredients alkylphenol ethoxylates and 4,5-methyl-1H-henzotriazoles

Characterization of the effects of aircraft deicer and anti-icer fluid (ADAF) runoff on aquatic organisms in receiving streams is a complex issue because the identities of numerous toxic additives are proprietary and not publicly available. Most potentially toxic and endocrine disrupting effects caused by ADAF are due to the numerous additive package ingredients which vary among manufacturers and types of ADAF formulation. Toxicity investigations of nine ADAF formulations indicate that endpoint concentrations for formulations of different manufacturers are widely variable. Type IV ADAF (anti-icers) are more toxic than Type I (deicers) for the four organisms tested (Vibrio fischeri, Pimephales promelas, Ceriodaphnia dubia, and Selenastrum capricornutum). Acute toxicity endpoint concentrations ranged from 347 to 7700 mg/L as ADAF for Type IV and from 1550 to 45,100 mg/L for Type I formulations. Chronic endpoint concentrations ranged from 70 to 1300 mg/L for Type IV and from 37 to 18,400 mg/L for Type I formulations. Alkylphenol ethoxylates and tolyltriazoles are two known classes of additives. Nonylphenol, nonylphenol ethoxylates, octylphenol, octylphenol ethoxylates, and 4,5-methyl-1H-benzotriazoles were quantified in the nine ADAF formulations, and toxicity tests were conducted with nonylphenol ethoxylates and 4,5-methyl-1H-benzotriazoles. Toxicity units computed for glycol and these additives, with respect to toxicity of the ADAF formulations, indicate that a portion of ADAF toxicity can be explained by the known additives and glycols, but much of the toxicity is due to unidentified additives.     

Winter-time climatic control on dissolved organic carbon export and surface water chemistry in an Adirondack forested watershed

Although most of forested watersheds in temperate and boreal regions are snow-covered for a substantial portion of the year, responses of biogeochemical processes under the snow pack to climatic fluctuations are poorly understood. We investigated responses of dissolved organic carbon (DOC) and surface water chemistry in stream and lake discharge waters draining the Arbutus Lake Watershed in the Adirondacks of New York State to climatic fluctuations during the snow-covered months from December through April. Interannual variability in stream discharge corresponded to changes in air temperature and snow pack depth across the winter months. Concentrations of DOC in stream water draining a subcatchment showed immediate positive responses to rising temperatures and subsequent increases in runoff during most snowmelt events. Increases in DOC concentrations usually coincided with decreases in pH and increases in total aluminum (Al) concentrations, while the correlations between concentrations of DOC and SO4(2-) or base cations were negative. Although changes in air temperature, snow pack depth, and runoff were all significantly correlated with stream water concentrations of major solutes, stepwise linear regression found that runoff was the best predictor of solute concentrations. Results of stepwise linear regression with long-term monthly monitoring data collected at the lake outlet showed weaker but still consistent climatic effects on interannual variations in concentrations of DOC and other solutes. Over the 17 winter periods from December 1983 through April 2000, changes in seasonal average concentrations of DOC, H+, and Al in lake discharge generally corresponded to interannual variations in temperature, precipitation, and runoff, while SO4(2-) and base cations displayed an opposite trend. The results suggest that snowmelt-mediated DOC responses to temperature fluctuations during the winter months might offset increases in the surface water pH caused by decreasing acidic deposition and pose a potential hazard of Al toxicity in surface waters.     

Organochlorine pesticide and polychlorinated biphenyl concentrations in snow, snowmelt, and runoff at Bow Lake, Alberta

We present analyses of the concentrations of organochlorine (OC) contaminants (including organochlorine pesticides and PCBs) in snow, snowmelt, and runoff in glacier and snowmelt fed streams at Bow Lake, Alberta in two contrasting hydrological years (1997 and 1998). The study investigates the variability in OC burdens in snow across the catchment, the elution of OCs from the snowpack, and the relationship between OC concentrations in streams and the annual snowpack. Snowpacks in forested sites were thinner and had lower OC concentrations than snowpacks in open or sparsely vegetated sites. The first snowmelt samples exhibited very high contaminant concentrations relative to the snowpack, and even the more hydrophobic compounds (Dieldrin, DDTs, and PCBs) were highly concentrated in meltwater. Interannual changes in the mean OC concentrations in streams did not reflect year-to-year changes in the snowpack contaminant concentrations. The results indicate that the extent of glacial ice melt may be more important than mean snowpack burdens as a control on OC concentrations in runoff in glacial catchments.     

Traffic as a source of organophosphorus flame retardants and plasticizers in snow

Snow samples collected in northern Sweden at a road intersection and an airport indicated that traffic is a source of organophosphorus flame retardants and plasticizers (OPs) in the outdoor environment. Analysis of snow samples taken at distances of 2, 100, and 250 m from the road intersection showed that the total amount of OPs declined as distance increased. Of the 11 analyzed substances, tris-(2-chloroisopropyl) phosphate (TCPP) dominated in the snow samples from the intersection, with levels of 170, 130, and 110 ng/kg snow at distances of 2, 100, and 250 m. Similar amounts of TCPP were found at the airport (100-220 ng/kg). These levels are approximately twice as high as the level found in the reference snow sample from a remote area (70 ng/kg). A possible explanation for the higher levels of TCPP found close to the road intersection is that it may be emitted from the interior of cars via their ventilation systems. Triphenyl phosphate (TPP) was identified in lubricants and in waste oil from vehicles, and thus, leakage of transmission and motor oils is a probable source of TPP found at the sampled sites. Ten OPs were detected in the three samples from the airport, of which tributyl phosphate (TBP) was the most abundant, at levels 3 orders of magnitude higher than in the reference sample, that is, 25 000 compared to 19 ng/kg. The main source of TBP at the airport was traced to aircraft hydraulic fluid. Analysis of background air and deposition samples indicated that some OPs are subject to long-range air transportation.     

Changes in surface area and concentrations of semivolatile organic contaminants in aging snow

During the winter of 1999/2000 five snowpacks at Turkey Lake Watershed east of Lake Superior were sampled immediately after falling and again after several days of aging for the analysis of specific snow surface area and the concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The snow surface could be determined with a relative coefficient of variation of 6% using frontal chromatography, measuring the retention of ethyl acetate, a substance with known adsorption coefficient on the ice surface. The snow surface area of fresh snow varied from 1000 to 1330 cm2/g and was higher for snow falling during colder days. The aged snow samples had consistently lower surface areas ranging from 520 to 780 cm2/g, corresponding to an average loss of half of the initial surface area during aging. The rate of loss of surface area was faster at higher temperatures. Dieldrin, alpha-HCH, and gamma-HCH were the most abundant OCPs in snowmelt water, but endosulfan, chlordane-related substances, heptachlor epoxide, pp'-DDT, pp'-DDE, and chlorinated benzenes were also consistently present. Three midwinter snowpacks that aged during relatively cold temperatures generally experienced a loss of PCBs and OCPs that was of the same order of magnitude as the observed loss of snow surface area. However, no relationship between the extent of loss and the strength of a contaminants' sorption to snow was apparent. Few significant changes in snowpack concentrations of OCPs and PCBs were observed in a snowpack that fell at relatively high temperatures and aged under colder conditions. Concentrations of OCPs and PCBs increased in a late-winter snowpack that aged while temperatures rapidly increased to above freezing. Concentrations of pp'-DDE and endosulfan-II that increased in snowpacks that saw simultaneous decreases in the levels of pp'-DDT and endosulfan-I hint at the occurrence of sunlight induced conversions in snow. While surface area decreases clearly contribute to the loss of semivolatile organic compounds from metamorphosing snowpacks, other confounding factors play a role in determining concentration changes, in particular in wet snow.     

Fate of perfluorinated carboxylates and sulfonates during snowmelt within an urban watershed

The transport dynamics of perfluorinated carboxylic acids and sulfonates during snowmelt in the highly urbanized Highland Creek watershed in Toronto, Canada was investigated by analyzing river water, bulk snow, and groundwater, sampled in February and March 2010, by means of liquid chromatography-tandem mass spectrometry. Perfluorohexanoate, perfluorooctanoate, and perfluorooctane sulfonate were dominant in river water, with concentrations of 4.0-14 ng·L(-1), 2.2-7.9 ng·L(-1), and 2.1-6.5 ng·L(-1), respectively. Relatively high levels of perfluorohexanoate may be related to the recent partial replacement in various consumer products of perfluorooctyl substances with shorter-chained perfluorinated compounds (PFCs). Highest PFC concentrations were found within the more urbanized part of the drainage area, suggestive of residential, industrial, and/or traffic-related sources. The riverine flux of PFCs increased during the snowmelt period, but only approximately one-fifth of the increased flux can be attributed to PFCs present in the snowpack, mostly because concentration in snow are generally quite low compared to those in river water. The remainder of the increased flux must be due to the mobilization of PFCs by the high flow conditions prevalent during snowmelt. Run-off behavior was clearly dependent on perfluoroalkyl chain length: Dilution with relatively clean snowmelt water caused a drop in the river water concentrations of short-chain PFCs at high flow during early melting. This prevented an early concentration peak of those water-soluble PFCs within the stream, as could have been expected in response to their early release from a melting snowpack. Instead, concentrations of particle-associated long-chain PFCs in creek water peaked early in the melt, presumably because high flow mobilized contaminated particles from impervious surfaces in the more urbanized areas of the watershed. The ability to enter the subsurface and deeper groundwater aquifers increased with the PFCs' water solubility, that is, was inversely related to perfluoroalkyl chain length.     

乙二醇葡糖苷的分离纯化

以葡萄糖和乙二醇为原料,以磷酸为催化剂,制备了乙二醇葡糖苷。采用萃取的方法对乙二醇葡糖苷进行初步分离,再用G15交联葡聚糖凝胶进行层析柱分离,以质量分数0.2‰的迭氮化钠溶液做流动相,体积流量为0.9 mL/min,可使乙二醇与乙二醇葡糖苷完全分离,实现除去乙二醇的目的。     

烷基酚聚氧乙烯醚的生态环保问题探讨

广泛使用的烷基酚聚氧乙烯醚(APEO)的生态环保问题在近20年受到争议。过去一直认为APEO的代谢物具有毒性，生物降解性差。本文综述近年来通过野外取样测试评定，得出相反结论。APEO及其代谢物的雌激素效应非常低，所有这些都不足以危害生态环境；但必须注意生产过程中副产物的危害性，有可能存在于某些企业的产品中。     

Simulating the influence of snow on the fate of organic compounds

Snow scavenging, a seasonal snowpack, and a dynamic water balance are incorporated in a non-steady-state generic multimedia fate model in order to investigate the effect of snow on the magnitude and temporal variability of organic contaminant concentrations in various environmental media. Efficient scavenging of large nonpolar organic vapors and particle-bound organic chemicals by snow can lead to reduced wintertime air concentrations and incorporation in the snowpack. The snow cover functions as a temporary storage reservoir that releases contaminants accumulating over the winter during a short melt period, resulting in temporarily elevated concentrations in air, water, and soil. The intensity of these peaks increases with the length of the snow accumulation period. Organic chemicals of sufficient volatility (log KOA < 9; e.g., light polychlorinated biphenyls) can volatilize from the snowpack, resulting in springtime concentration maxima in the atmosphere. The behavior of fairly water-soluble chemicals during snowmelt depends on their relative affinity for the newly formed liquid water phase and the rapidly diminishing ice surface-quantitatively expressed by their interface-water partition coefficient (KIW). Chemicals with a preference for the dissolved phase (low KIW; e.g., pentachlorophenol) can become enriched in the first meltwater fractions and experience a temporary concentration peak in lakes and rivers. Organic chemicals that are neither volatile enough to evaporate from the snowpack nor sufficiently water soluble to dissolve in the meltwater (e.g., polybrominated diphenyl ethers) sorb to the particles in the snowpack. These particles may be sufficiently contaminated to constitute the major input route to the terrestrial environment upon release during snowmelt. Because wintertime deposition to the snowpack may be higher than to a non-snow covered surface, this can result in higher soil concentrations of persistent organic contaminants in the long term. The potential ecotoxicological significance of peak exposures demands a better understanding of the role of snow in the fate of organic contaminants.     

Benzotriazole and tolyltriazole as aquatic contaminants. 1. Input and occurrence in rivers and lakes

The complexing agents benzotriazole (BT) and tolyltriazole (TT) are not only widely applied as anticorrosives, e.g., in aircraft deicer and anti-icer fluid (ADAF), but they are also used for so-called silver protection in dishwasher detergents. Due to their low biodegradability and limited sorption tendency, BT and TT are only partly removed in wastewater treatment. Residual concentrations of BT and TT were determined in ambient surface waters in Switzerland including 7 rivers which have distinct water flows and receive treated wastewater effluents at various dilution ratios. A maximum BT concentration of 6.3 microg/L was found in the Glatt River, and a maximum mass flow of 277 kg BT per week was observed in the Rhine River. In most cases, TT was about a factor 5-10 less abundant. During winter 2003/4, BT mass flows at 2 locations in the lower stretch of the Glatt River clearly indicated the input from nearby Zurich airport, where BT was applied as an anticorrosive ADAF component. BT concentrations measured in the three lakes Greifensee, Lake Zurich, and Lake Geneva were approximately 1.2, 0.1-0.4, and 0.2 microg/L, respectively. The observed environmental occurrences indicate that BT and TT are ubiquitous contaminants in the aquatic environment and that they belong to the most abundant individual water pollutants.     

Some sources and sinks of monomethyl and inorganic mercury on Ellesmere Island in the Canadian High Arctic

We identified some of the sources and sinks of monomethyl mercury (MMHg) and inorganic mercury (HgII) on Ellesmere Island in the Canadian High Arctic. Atmospheric Hg depletion events resulted in the deposition of Hg(II) into the upper layers of snowpacks, where concentrations of total Hg (all forms of Hg) reached over 20 ng/L. However, our data suggest that much of this deposited Hg(II) was rapidly photoreduced to Hg(0) which then evaded back to the atmosphere. As a result, we estimate that net wet and dry deposition of Hg(II) during winter was lower at our sites (0.4-5.9 mg/ha) than wet deposition in more southerly locations in Canada and the United States. We also found quite high concentrations of monomethyl Hg (MMHg) in snowpacks (up to 0.28 ng/L), and at times, most of the Hg in snowpacks was present as MMHg. On the Prince of Wales Icefield nearthe North Water Polynya, we observed a significant correlation between concentrations of Cl and MMHg in snow deposited in the spring, suggesting a marine source of MMHg. We hypothesize that dimethyl Hg fluxes from the ocean to the atmosphere through polynyas and open leads in ice, and is rapidly photolyzed to MMHgCl. We also found that concentrations of MMHg in initial snowmelt on John Evans Glacier (up to 0.24 ng/L) were higher than concentrations of MMHg in the snowpack (up to 0.11 ng/L), likely due to either sublimation of snow or preferential leaching of MMHg from snow during the initial melt phase. This springtime pulse of MMHg to the High Arctic, in conjunction with climate warming and the thinning and melting of sea ice, may be partially responsible for the increase in concentrations of Hg observed in certain Arctic marine mammals in recent decades. Concentrations of MMHg in warm and shallow freshwater ponds on Ellesmere Island were also quite high (up to 3.0 ng/L), leading us to conclude that there are very active regions of microbial Hg(II) methylation in freshwater systems during the short summer season in the High Arctic.     

APEO的限用和对我国纺织助剂的影响

按照欧盟法则2003／53／EG，从2005年1月17日起欧洲对APE0的使用进行了严格的限制。文章阐述了APEO的危害性及我国生产、使用、检测APEO的状况，提出了相应的取代产品，强调必须加大替代品研究和开发力度。     

红外光谱对纺织助剂中烷基酚聚氧乙烯醚的快速定性和定量

为快速排查纺织助剂中APEO,建立了红外光谱对纺织助剂中APEO的定性和定量方法。应用红外二阶导数谱图中1608±4cm-1, 1510±3 cm-1一组特征吸收峰筛查纺织助剂中不同分子结构形式的APEO。红外光谱对APEO的定性方法不需标准品、不需对样品进行分离,简单快速。同时,应用定量软件TQ Analyst中的偏最小二乘法,选择二阶导数红外光谱并选取（1529.27cm-1,1496.45cm-1）峰范围建立APEO定量模型,回归系数R为0.99946,均方根误差RMSEC为0.970。应用该定量模型对APEO定量,结果显示其绝对偏差在-1.56~3.18%范围, 回收率为82~117%。     

Measuring the release of organic contaminants from melting snow under controlled conditions

The release of organic contaminants from a melting snowpack may result in temporary concentration peaks in receiving water bodies and respective pulse exposure of aquatic organisms. It is thus of considerable interest to gain a mechanistic and quantitative understanding of the processes determining the dynamic behavior of organic chemicals during snowmelt. Uniformly structured and contaminated snow was produced with the help of a newly designed snow gun and exposed to predetermined temperature conditions in a temperature-controlled cold room. The dry density and liquid water content during four freeze-thaw cycles was recorded continuously at different layers within the snowpack using time domain reflectometry, providing information on meltwater production and propagation as well as snow metamorphism. Fractionated meltwater samples were filtered and the dissolved and particle phase analyzed for five polycyclic aromatic hydrocarbons (PAHs) using gas chromatography/ mass spectrometry. The distribution of the PAHs between the dissolved and particulate fractions of the meltwater was strongly related to their hydrophobicity. Particle-bound PAHs were released late during the snowmelt, whereas PAHs in the dissolved phase were released uniformly during a two day melting period. Even though conductivity measurements indicated a preferential early elution of ions in the first meltwater fractions, no such "first flush" behavior was observed for soluble PAH. The developed laboratory-based approach opens up for the first time the possibility of reproducible experiments on organic contaminant behavior in snow. Future experiments will explore, in detail, how the properties of organic chemicals, the physical and chemical properties of the snowpack, and the temperature variations before and during the time of melting interact to determine the timing of chemical release from a snowpack.     

烷基酚聚氧乙烯醚的识别与合规要点

烷基酚聚氧乙烯醚(APEO)是一类广泛应用于纺织、印染、制革等行业的双亲型非离子表面活性剂,因应用于纺丝、织布、前处理、染色、印花、后整理等多个环节,为其识别和替代带来不少困难.由于APEO的毒性,各国政府、服装鞋类品牌、国际性行业协会都对其采取禁用或限用措施.回顾了APEO的应用现状、各个国家的法律法规、在纺织染整行...     

Perfluorinated acids in air, rain, snow, surface runoff, and lakes: relative importance of pathways to contamination of urban lakes

Concentrations of perfluorinated acids (PFAs) were measured in various environmental matrices (air, rain, snow, surface runoff water, and lake water) in an urban area, to enable identification of sources and pathways of PFAs to urban water bodies. Total PFA concentrations ranged from 8.28 to 16.0 pg/ m3 (mean 11.3) in bulk air (sum of vapor and particulate phases), 0.91 to 13.2 ng/L (6.19) in rainwater, 0.91 to 23.9 ng/L (7.98) in snow, 1.11-81.8 ng/L (15.1 ng/L) in surface runoff water (SRW), and 9.49 to 35.9 ng/L (21.8) in lake water. Perfluorooctanoic acid (PFOA) was the predominant compound, accounting for > 35% of the total PFA concentrations, in all environmental matrices analyzed. Concentrations and relative compositions of PFAs in SRW were similar to those found for urban lakes. SRW contributes to contamination by PFOA in urban lakes. The measured concentration ratios of FTOH to PFOA in air were 1-2 orders of magnitude lower than the ratios calculated based on an assumption of exclusive atmospheric oxidation of FTOHs. Nevertheless, the mass balance analysis suggested the presence of an unknown input pathway that could contribute to a significant amount of total PFOA loadings to the lake. Flux estimates of PFOA at the air-water interface in the urban lake suggest net volatilization from water.     

纺织印染助剂中APEO的环保替代

烷基酚聚氧乙烯醚（APEO）是多年来常用的非离子表面活性剂，广泛应用于纺织印染助剂的生产．由于APEO存在毒性大、生物降解性差和环境激素等生态安全性问题，其禁用已引起全人类的重视．积极开发和使用替代APEO的环保表面活性剂并应用于纺织印染助剂的研究及生产工作已刻不容缓．     

Starch-Polyvinyl Alcohol Films –Effect of Various Plasticizers

Various polyols were evaluated as plasticizers for starch-polyvinyl alcohol films. Glycol glycoside, an experimental polyol made from starch and ethylene glycol, and sorbitol were highly effective plasticizers alone and in combination with small amounts of glycerol. Glycol glycoside is an especially attractive plasticizer because of its low production cost. Glucose and sucrose performed well in combination with glycerol or sorbitol.     

APEO的禁用与环保替代

APEO（烷基酚聚氧乙烯醚）是继脂肪醇聚氧乙烯醚之后的另一大类非离子表面活性剂,具有性质稳定、耐酸碱、成本低等特征,广泛应用于纺织印染领域.但由于APEO的生态环保问题,欧盟等地区对纺织品的APEO已有限量的要求,因此,纺织印染助剂中APEO的环保替代工作刻不容缓.