Calculating the aquatic toxicity of hydrocarbon mixtures

For acute toxicity to aquatic organisms, individual hydrocarbons are equally toxic on the basis of their internal molar concentration within the organism. The differences in measured toxicities among hydrocarbons lies with differences in their equilibrium partitioning behavior between water and the organism. For complex hydrocarbon mixtures, an additional complication of partitioning between the bulk hydrocarbon and the water is encountered. Equations are developed for calculating the water concentration of components of complex hydrocarbon mixtures. Using gasoline as an example, a method is presented for first calculating the concentration of gasoline components in water after equilibration with different gasoline volumes and then, the component toxicities are used to estimate the gasoline volume causing 50% mortality to aquatic organisms.     

Risk assessment approach for untreated wastewater using the QUAL2E water quality model

This paper presents a novel approach for assessing the risk of consumer product ingredients in surface waters that receive untreated wastewater. The approach utilizes the water quality simulation model QUAL2E for predicting the impact caused by conventional pollutants, as well as the exposure concentration of consumer product ingredients. This approach invokes an impact zone concept whereby the receiving water can be thought of as a natural wastewater treatment system. After the river has recovered via self-purification, the ecosystem is then assessed by traditional risk assessment methods. This approach was validated using data collected from the Balatuin River, which is located in the Philippines. Results from this study support the use of QUAL2E for assessing the risk of consumer product ingredients in riverine systems receiving untreated wastewater.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

A theoretical investigation of the pressure and temperature dependence of atmospheric ozone deposition to trees

Methods for describing the exposure patterns of forests to atmospheric ozone concentrations are compared with special emphasis on the situation at high altitudes, such as the Appalachian Mountains of the eastern USA. Limitations to the use of ozone concentration as mass per unit volume are discussed and a correction for temperature and pressure changes is derived. If identical ozone mass concentrations were measured at two sites separated by 2000 m elevation, the ozone flux at the lower site would exceed the flux at the higher site by 4-8% due to temperature and pressure effects on both air volume and ozone deposition velocity. It is recommended that ozone exposures be described in terms of 'flux-corrected' mass concentrations or volumetric mixing ratios when ambient ozone data from sites at different altitudes are to be compared.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

An Air Quality Data Analysis System for Interrelating Effects,Standards, and Needed Source Reductions: Part 6. Calculating Concentration Reductions Needed to Achieve the New National Ozone Standard

The new ozone National Ambient Air Quality Standard specifies that the expected number of days per calendar year that the 1 hour average ozone concentration can exceed 0.12 ppm must be equal to or less than 1. This paper describes a method to calculate design frequency, design concentration, and the percentage concentration reduction necessary to achieve this standard. The design frequency is once per year (1/365) if daily maximum hour ozone concentrations are available at a particular site for an equal number of days in summer (April through September) and winter (October through March). An equation is used to adjust design frequency as a function of the number of summer and winter samples available. The design concentration (the ambient concentration measured at the design frequency) needs to be reduced to 0.12 ppm. Graphical and digital methods for determining the design concentration are presented. Percentage concentration reductions needed to achieve the standard are calculated for each site which has ozone concentration data available in the National Aerometric Data Bank for at least half of the days in one summer of years 1975 through 1977. The degree of reduction calculated for the site with the highest concentrations in each county is indicated by shading on a map of the United States.     

Comparison of atmosphere/aquatic environment concentration ratio of volatile chlorinated hydrocarbons between temperate regions and Antarctica

For the purpose of understanding the transport and deposition mechanisms and the air–water distribution of some volatile chlorinated hydrocarbons (VCHCs), their atmosphere/aquatic environment concentration ratio was evaluated. In addition, for the purpose of differentiating VCHC behaviour in a temperate climate from its behaviour in a polar climate, the atmosphere/aquatic environment concentration ratio evaluated in matrices from temperate zones was compared with the concentration ratio evaluated in Antarctic matrices.In order to perform air samplings also at rigid Antarctic temperatures, the sampling apparatus, consisting of a diaphragm pump and canisters, was suitably modified.Chloroform, 1,1,1-trichloroethane, tetrachloromethane, 1,1,2-trichloroethylene and tetrachloroethylene were measured in air, water and snow using specific techniques composed of a purpose-made cryofocusing-trap-injector (for air samples) and a modified purge-and-trap injector (for aqueous samples) coupled to a gas chromatograph with mass spectrometric detection operating in selected ion monitoring mode. The VCHCs were retrieved in all the investigated matrices, both Italian and Antarctic, with concentrations varying from tens to thousands of ng m⁻³ in air and from digits to hundreds of ng kg⁻¹ in water and snow.The atmosphere/aquatic environment concentration ratios were always found to be lower than 1. In particular, the Italian air/water concentration ratios were smaller than the Antarctic ones, by reason of the higher atmospheric photochemical activity in temperate zones. On the other hand, the Antarctic air/snow concentration ratios proved to be largely in favour of snow with respect to the Italian ratios, thus corroborating the hypothesis of a more efficient VCHC deposition mechanism and accumulation on Antarctic snow.     

Peracetic acid disinfection: a feasible alternative to wastewater chlorination.

The paper summarizes the results of a bench-scale study to evaluate the feasibility of using peracetic acid (PAA) as a substitute for sodium hypochlorite both for discharge into surface water and for agricultural reuse. Trials were carried out with increasing doses (1, 2, 3, 5, 10, and 15 mg/L) and contact times (6, 12, 18, 36, 42, and 54 minutes) to study disinfectant decay and bacterial removal and regrowth, using fecal coliform and Escherichia coli (E. coli) as process efficiency indicators. Peracetic acid decay kinetics was evaluated in tap water and wastewater; in both cases, PAA decays according to first-order kinetics with respect to time, and a correlation was found between PAA oxidative initial consumption and wastewater characteristics. The PAA disinfection efficiency was correlated with operating parameters (active concentration and contact time), testing different kinetic models. Two data groups displaying a different behavior on the basis of initial active concentration ranges (1 to 2 mg/L and 5 to 15 mg/L, respectively) can be outlined. Both groups had a "tailing-off" inactivation curve with respect to time, but the second one showed a greater inactivation rate. Moreover, the effect of contact time was greater at the lower doses. Hom's model, used separately for the two data groups, was found to best fit experimental data, and the disinfectant active concentration appears to be the main factor affecting log-survival ratios. Moreover, the S-model better explains the initial resistance of E. coli, especially at low active concentrations (< 2 mg/L) and short contact times (< 12 minutes). Microbial counts, performed by both traditional methods and flow cytometry, immediately and 5 hours after sample collection (both with or without residual PAA inactivation), showed that no appreciable regrowth took place after 5 hours, neither for coliform group bacteria, nor for total heterotrophic bacteria.     

Synthesis of high-purity Na-A and Na-X zeolite from coal fly ash

Coal fly ash (CFA) was used as a raw material for the synthesis of zeolite molecular sieve. The synthesis began with the pretreatment of CFA to remove impurities (e.g., Fe₂O₃, CaO, etc.) under various acid types (HCl, H₂SO₄, and HNO₃) and acid/CFA ratios (5–25 mL_acid/g_CFA). High product purity (up to 97%) was achieved with HCl (20%wt), and acid/CFA ratio of 20 mL_HCl/g_CFA. The treated CFA was then converted to zeolite by the fusion reaction under various Si/Al molar ratios (0.54–1.84). Zeolite type A was synthesized when the Si/Al molar ratios were lower than 1, whereas sodium aluminum silicate hydrate was formed when the Si/Al molar ratio were higher than 1. The highest water adsorption performance of the zeolite product, i.e., the outlet ethanol concentration of 99.9%wt and the specific adsorption capacity of 2.31 × 10^?2 g_water/g_zeolite, was observed with the Si/Al molar ratio of 0.82. The zeolite was tested for its water adsorption capacity repeatedly 10 times without deactivation.

Implications: This work evaluated the technical feasibility in the conversion of CFA to zeolite, which would help reduce the quantity of waste needed to be landfilled. This adds value to the unwanted material by converting it into something that can be further used. The synthesized products were shown to be quite stable as water adsorbent for the dehydration of ethanol solution.     

Changes in concentration of five PCDD/F congeners after cooking beef from treated cattle

A large piece of meat taken from a single animal, which had been dosed with five selected PCDD/Fs, was prepared and cooked by a selection of different methods; burgers (fried, grilled, barbecued), roasts (cooked using conventional and microwave ovens) and stews (open pan and pressure cooked). For some of the cooking methods, concentration changes, on a whole product basis, were observed between raw and cooked product. However, in all cases these could be explained simply through changes arising from loss of water and elimination of PCDD/Fs with released fat. The total amounts of PCDD/Fs present in the system (including in released fat) remained unchanged. Dietary intake of PCDD/Fs could therefore be reduced by the removal of visible fat from meat before cooking and by discarding any fat released from foods during the cooking process.     

Analysis of chemical compositions contributable to chemical oxygen demand (COD) of oilfield produced water

This work was to give a comprehensive estimation for the chemical compositions contributable to COD of the produced water treatment system. For this purpose, the wastewater samples were collected from an onshore wastewater treatment plant. The chemical compositions of the wastewater were investigated, and the COD contributed by each component was estimated. The results showed that the COD levels of O&G and SS presented decreasing trends during the whole process and achieved total removal percentages of 95.1% and 62.3%, respectively. The final COD of organic acids and low-molecular-weight carbonyl compounds were respectively lowered to nearly 64% and 35% of their initial levels, and no regular trends were found for the COD of these chemicals during the whole treatment process. The COD of inorganic components presented minor variations at all sampling spots. The majority of COD was originated from O&G in raw wastewater. The COD contributed by O&G decreased greatly with continuous treatment and finally was lower than 17% of measured COD. At each sampling spot, the ratios of COD contributed by SS did not exceed 7.6% of measured COD. Other measured chemicals, including organic acids, carbonyl compounds, volatile phenols, reductive anions, metals and TDP were not the main sources of COD during the whole treatment process, and the ratio of COD was below 9% at each sampling spot. Most of the soluble components contributable to residual COD were still unknown after biological treatment, and the COD contributed by these components was greater than 57% of measured COD.     

Hydrophobicity of complex organic mixtures

Hydrophobicity is an important property in risk assessment of chemicals. A group parameter that reflects the hydrophobicity of technical mixtures is not yet available. However, many substances are complex organic mixtures, for which it is practically impossible to determine each component separately. An experimental procedure to measure the hydrophobicity of organic mixtures without knowledge of the individual components was developed and tested for a mixture of benzene and twelve chlorobenzenes. This procedure is based on separation of the mixture into fractions of increasing hydrophobicity by reversed-phase HPLC, after which the total molar concentration in each fraction is determined by vapour pressure osmometry. The obtained information on hydrophobicity can be used for assessing bioaccumulation and sediment sorption after emission of the mixture to water has occurred.     

水碳比变化对汽油氧化重整制氢影响的研究

本文用正辛烷代替汽油从理论和实验两方面研究了水碳比变化对汽油氧化重整制氢反应的影响。理论研究表明 ,在绝热反应条件下 ,对应确定的反应温度存在一个最佳的氧油比及水碳比 ;实验研究表明 ,在非绝热反应体系中 ,在一定的氧油比及反应温度条件下 ,反应体系的转化率及生成氢的选择性均随水碳比的增加而增加 ,为实现燃料电池汽油制氢自热反应 ,反应体系应在一定水碳比条件下进行 ,实验条件下最佳的水碳比范围是 1.5— 2 .5之间。     

Evaluating the exchange of DDTs between sediment and water in a major lake in North China

A large-scale sampling program was conducted to simultaneously collect surface water, overlying water, pore water, and sediment samples at monthly intervals between March and December 2010 from Baiyangdian Lake, North China to assess the distribution of DDTs and determine the net direction of sediment–water exchange. Total DDT concentrations ranged 2.36–22.4 ng/L, 0.72–21.9 ng/L, 2.25–33.7 ng/L, and 4.42–7.29 ng/g in surface water, overlying water, pore water, and sediments, respectively, which were at the intermediate levels compared to those of other area around the world. Seasonal variations of DDTs were featured by higher concentration in summer. This was likely associated with (a) the increase of land runoff in the summer and (b) application of dicofol and DDT-containing antifouling paints for ships in summer. Sediment–water fugacity ratios of the DDT isomers were used to predict the direction of the sediment–water exchange of these isomers. The sediment–surface water, sediment–overlying water, and sediment–pore water fugacity ratios of DDT isomers averaged 0.34, 0.44, and 0.1, which are significantly lower than the equilibrium status (1.0), suggesting that the net flux direction were from the water to sediment and the sediment acted as a sink for the DDTs. The difference of DDT concentrations between sediment and water samples was found to be an important factor affecting the diffusion of DDT from the water to sediment.     

Temporal and spatial variation of RNA content in nymphs of the mayfly, Stenonema femoratum (Say)

Temporal variation of RNA: weight, RNA: protein, RNA: DNA, and protein: DNA ratios in Stenonema femoratum (Say) was assessed by monitoring at the same site in a small midwestern stream over a two-year period. Variation components were estimated using a two-way mixed model analysis of variance with weight class and collection date as main effects. About 30% of the variation in RNA concentration was within-cell variation associated with differences among individuals and analytical error. Temporal variation accounted for about 50% of the total variability in RNA concentration data. RNA: weight had 11% and RNA: protein had 17% variation attributed to weight class effects indicating that these ratios were dependent on the size of the mayfly. RNA: DNA ratios were not influenced by mayfly weight, suggesting that this ratio would be the most appropriate for comparing populations based on means of mixed individual sizes. Comparison of mean RNA: DNA ratios among collection dates yielded significant increases in the ratio during late fall in two consecutive years. Spatial variations in RNA: DNA ratios of S. femoratum collected from sites of similar habitats were not significantly different. These data encourage the future development of RNA concentration as an in situ biochemical indicator of growth rate and possibly of stress related effects on growth rate.     

Preparing to measure the effects of the NOx SIP call--methods for ambient air monitoring of NO,NO2, NOy,and individual NOz species

The capping of stationary source emissions of NOx in 22 states and the District of Columbia is federally mandated by the NOx SIP Call legislation with the intended purpose of reducing downwind O3 concentrations. Monitors for NO, NO2, and the reactive oxides of nitrogen into which these two compounds are converted will record data to evaluate air quality model (AQM) predictions. Guidelines for testing these models indicate the need for semicontinuous measurements as close to real time as possible but no less frequently than once per hour. The measurement uncertainty required for AQM testing must be less than +/-20% (+/-10% for NO2) at mixing ratios of 1 ppbv and higher for NO, individual NOz component compounds, and NOy. This article is a review and discussion of different monitoring methods, some currently used in research and others used for routine monitoring. The performance of these methods is compared with the monitoring guidelines. Recommendations for advancing speciated and total NOy monitoring technology and a listing of demonstrated monitoring approaches are also presented.     

The occurrence of disinfection by-products in the drinking water of Athens,Greece

Application of chlorination for the disinfection of drinking water results in the formation of a wide range of organic compounds, called disinfection by-products (DBPs), which occur due to the reaction of chlorine with natural organic materials. The occurrence of DBPs was studied in samples from four drinking-water treatment plants (WTPs) and from the distribution network of Athens, Greece. Twenty-four compounds, which belong to different categories of DBPs, were monitored, including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HAKs), chloral hydrate (CH) and chloropicrin (CP). Sampling was performed monthly for a period of two years, from three different points at each WTP and from eight points atthe distribution network. Samples were analyzed by GC-ECD methods, which included pretreatment with liquid-liquid extraction for volatile DBPs and acidic methanol esterification for HAAs. The results of the analyses have shown the presence of disinfection by-products belonging to all categories studied in all water samples collected after prechlorination. The major categories of DBPs detected were THMs and HAAs, while the other volatile DBPs occurred at lower concentrations. The concentrations of DBPs did not in any case exceed the maximum contaminant levels (MCL) set by USEPA and WHO. However, monitoring these compounds needs to be continued, because their levels could increase due to changes in the quality of water entering the water treatment plants. Reduction of the concentrations of DBPs could be achieved by optimization of the chlorination conditions, taking into account the effect of time. Moreover, research on alternative disinfection methods (e.g. ozone, chlorine dioxide, chloramines) and their by-products should be conducted to evaluate their applicability in the case of the drinking water of Greece.     

A sensitivity study of separation distances calculated with the Austrian Odour Dispersion Model (AODM)

The Austrian Odour Dispersion Model (AODM) is a Gaussian model adapted for the prediction of odour sensation. It estimates the daily and seasonal variation of the odour emission, the average, ambient odour concentration and the momentary (peak) concentration for the time-interval of a single human breath (approx. 5 s). Peak concentrations, further downwind, are modified by use of an exponential attenuation function for which the ratios of the standard deviations of the wind components to the average wind speed have either to be taken from the literature or to be calculated, e.g. from ultrasonic anemometer data.AODM calculates direction-dependent separation distances for a combination of odour threshold and exceedence probability, which are a function of the prevailing wind velocity and atmospheric stability conditions. Meteorological time series from one site in Styria in southern Austria and one site in the Austrian flatlands, North of the Alps, both rural, are used for a sensitivity study of separation distances. One aspect is, how two different schemes to determine atmospheric stability influence the separation distances. Another source of uncertainty of the calculated separation distances results from the use of measured or literature values for the ratios mentioned above. Decisions on which schemes or ratios to be used have a decisive influence on the separation distances.     

Seasonal and spatial variation of diffuse (non-point) source zinc pollution in a historically metal mined river catchment, UK

Quantifying diffuse sources of pollution is becoming increasingly important when characterising river catchments in entirety - a prerequisite for environmental management. This study examines both low and high flow events, as well as spatial variability, in order to assess point and diffuse components of zinc pollution within the River West Allen catchment, which lies within the northern England lead-zinc Orefield. Zinc levels in the river are elevated under all flow regimes, and are of environmental concern. Diffuse components are of little importance at low flow, with point source mine water discharges dominating instream zinc concentration and load. During higher river flows 90% of the instream zinc load is attributed to diffuse sources, where inputs from resuspension of metal-rich sediments, and groundwater influx are likely to be more dominant. Remediating point mine water discharges should significantly improve water quality at lower flows, but contribution from diffuse sources will continue to elevate zinc flux at higher flows.