Evidence for the "grasshopper" effect and fractionation during long-range atmospheric transport of organic contaminants

Although there is indisputable evidence that long-range atmospheric transport (LRAT) of organic contaminants occurs on a global scale, uncertainties remain about the detailed mechanism and extent of this phenomenon as well as the physical-chemical properties which facilitate LRAT. In this study, we discuss how mass balance models and monitoring data can contribute to a fuller understanding of the mechanism and extent of LRAT. Specifically we address the issues of "grasshopping" or "hopping" (the extent to which molecules are subject to multiple hops as distinct from a single emission-deposition event) and "global fractionation" (the differing behavior of chemicals as they are transported). It is shown that simple mass balance models can be used to assist the interpretation of monitoring data while also providing an instrument that can be used to assess the LRAT potential and the extent of hopping that organic substances may experience. The available evidence supports the notion that many persistent organic pollutants experience varying degrees of "hopping" during their environmental journey and as a consequence become fractionated with distance from source.     

香港区域发展策略性环境影响评价的实践探讨

香港区域发展的策略性环境影响评价(简称环评)从20世纪80年代起步,已形成包括行政规定和法例规定的制度框架,其策略性环评的实践范围也逐步从规划、计划向政策、策略扩展.从评价过程、评价方法、公众参与时段安排、决策出发点等方面分析了2个香港区域发展的策略性环评案例.结果表明,为使策略性环评取得预想的成果并有助于可持续发展,...     

Degradation half-life times of PCDDs, PCDFs and PCBs for environmental fate modeling

Literature search of the knowledge on the degradation of persistent organic pollutants (POPs) in environmental compartments air, water, soil and sediment was done in purpose to find properties of POPs of interest for modeling. One degradation process, hydrolysis (chemical degradation), was omitted as negligibly slow for POPs studied. The other two, photolysis and biodegradation processes, were considered separately in purpose to develop estimation procedures. The estimates can be given as pseudo first-order rate constants kP for photolysis and kB for biodegradation. For each compartment, an overall degradation rate is k(tot) = kP + kB and lifetime t(1/2) = ln 2/k(tot). The latter values, lifetimes in each compartment, will be used as input parameters to the Baltic Sea model.     

Acute toxicity of aromatic and non-aromatic fractions of naphthenic acids extracted from oil sands process-affected water to larval zebrafish

The toxicity of oil sands process-affected water (OSPW) has regularly been attributed to naphthenic acids, which exist in complex mixtures. If on remediation treatment (e.g., ozonation) or on entering the environment, the mixtures of these acids all behave in the same way, then they can be studied as a whole. If, however, some acids are resistant to change, whilst others are not, or are less resistant, it is important to establish which sub-classes of acids are the most toxic.     

Co-injection of air and steam for the prevention of the downward migration of DNAPLs during steam enhanced extraction: an experimental evaluation of optimum injection ratio predictions

When steam is injected into soil containing a dense volatile non-aqueous phase liquid contaminant, the DNAPL vaporized within the heated soil region condenses and accumulates ahead of the steam condensation front. If enough DNAPL accumulates, gravitational forces can overcome trapping forces allowing the liquid contaminant to flow downward. By injecting air with steam, a portion of the DNAPL vapor remains suspended in equilibrium with the air, decreasing liquid contaminant accumulation ahead of the steam condensation front, and thus reducing the possibility of downward migration. In a previous work, a theoretical model was developed to predict the optimum injection ratio of air to steam that would eliminate accumulation of DNAPL ahead of the temperature front and thus minimize the potential for downward migration. In this work, the theoretical model is summarized, and an experiment is presented in order to evaluate the optimum injection ratio prediction. In the experiment, a two-dimensional water saturated sand pack is contaminated with a known mass of TCE (DNAPL). The system is then remediated by co-injecting air and steam at the predicted optimum injection ratio, calculated based on the average contaminant soil concentration in the sand pack. Results for the co-injection of air and steam are compared to results for the injection of pure steam or pure air. Injection at the predicted optimum injection ratio for a volumetric average NAPL saturation, reduced accumulation of the contaminant ahead of the condensation front by over 90%, as compared to steam injection alone. This indicates that the optimum injection ratio prediction is a valuable tool for limiting the spreading of DNAPL during steam-enhanced extraction. Injection at the optimum injection ratio resulted in earlier recovery of contaminant than for steam injection alone. Co-injection of steam and air is also shown to result in much higher recovery rates than air injection alone.     

The effects of crude oil and the effectiveness of cleaner application following oiling on US Gulf of Mexico coastal marsh plants

Field studies were conducted in two different marsh habitats in Louisiana coastal wetlands to evaluate the effects of oiling (using South Louisiana Crude oil, SLC) and the effectiveness of a shoreline cleaner (COREXIT 9580) in removing oil from plant canopies. The study sites represented two major marsh habitats; the brackish marsh site was covered by Spartina patens and the freshwater marsh was covered by Sagittaria lancifolia. Field studies were conducted in each habitat using replicated 5.8 m2 plots that were subjected to three treatments; oiled only, oiled + cleaner (cleaner was used 2 days after oiling), and a control. Plant gas exchange responses, survival, growth, and biomass accumulation were measured. Results indicated that oiling led to rapid reductions in leaf gas exchange rates in both species. However, both species in 'oiled + cleaned' plots displayed improved leaf conductance and CO2 fixation rates. Twelve weeks after treatment initiation, photosynthetic carbon fixation in both species had recovered to normal levels. Over the short-term, S. patens showed more sensitivity to oiling with SLC than S. lancifolia as was evident from the data of the number of live shoots and above-ground biomass. Above-ground biomass remained significantly lower than control in S. patens under 'oiled' and 'oiled + cleaned' treatments while it was comparable to controls in S. lancifolia. These studies indicated that the cleaner removed oil from marsh grasses and alleviated the short-term impact of oil on gas exchange function of the study plants. However, use of cleaner had no detectable effects on above-ground biomass production or regeneration at the end of the first growing season in S. patens. Similarly, no beneficial effects of cleaner on carbon fixation and number of live shoots were apparent beyond 12 weeks in S. lancifolia.     

Mechanisms of lead, copper, and zinc retention by phosphate rock

The solid-liquid interface reaction between phosphate rock (PR) and metals (Pb, Cu, and Zn) was studied. Phosphate rock has the highest affinity for Pb, followed by Cu and Zn, with sorption capacities of 138, 114, and 83.2 mmol/kg PR, respectively. In the Pb-Cu-Zn ternary system, competitive metal sorption occurred with sorption capacity reduction of 15.2%, 48.3%, and 75.6% for Pb, Cu, and Zn, respectively compared to the mono-metal systems. A fractional factorial design showed the interfering effect in the order of Pb>Cu>Zn. Desorption of Cu and Zn was sensitive to pH change, increasing with pH decline, whereas Pb desorption was decreased with a strongly acidic TCLP extracting solution (pH = 2.93). The greatest stability of Pb retention by PR can be attributed to the formation of insoluble fluoropyromorphite [Pb(10)(PO(4))(6)F(2)], which was primarily responsible for Pb immobilization (up to 78.3%), with less contribution from the surface adsorption or complexation (21.7%), compared to 74.5% for Cu and 95.7% for Zn. Solution pH reduction during metal retention and flow calorimetry analysis both supported the hypothesis of retention of Pb, Cu, and Zn by surface adsorption or complexation. Flow calorimetry indicated that Pb and Cu adsorption onto PR was exothermic, while Zn sorption was endothermic. Our research demonstrated that PR can effectively remove Pb from solutions, even in the presence of other heavy metals (e.g. Cu, Zn).     

Bacteria transport and deposition under unsaturated conditions: the role of the matrix grain size and the bacteria surface protein

Unsaturated (80% water saturated) packed column experiments were conducted to investigate the influence of grain size distribution and bacteria surface macromolecules on bacteria (Rhodococcus rhodochrous) transport and deposition mechanisms. Three sizes of silica sands were used in these transport experiments, and their median grain sizes were 607, 567, and 330 microm. The amount of retained bacteria increased with decreasing sand size, and most of the deposited bacteria were found adjacent to the column inlet. The deposition profiles were not consistent with predictions based on classical filtration theory. The experimental data could be accurately characterized using a mathematical model that accounted for first-order attachment, detachment, and time and depth-dependent straining processes. Visual observations of the bacteria deposition as well as mathematical modelling indicated that straining was the dominant mechanism of deposition in these sands (78-99.6% of the deposited bacteria), which may have been enhanced due to the tendency of this bacterium to form aggregates. An additional unsaturated experiment was conducted to better deduce the role of bacteria surface macromolecules on attachment and straining processes. In this case, the bacteria surface was treated using a proteolitic enzyme. This technique was assessed by examining the Fourier-transform infrared spectrum and hydrophobicity of untreated and enzyme treated cells. Both of these analytical procedures demonstrated that this enzymatic treatment removed the surface proteins and/or associated macromolecules. Transport and modelling studies conducted with the enzyme treated bacteria, revealed a decrease in attachment, but that straining was not significantly affected by this treatment.     

Source apportionment of polycyclic aromatic hydrocarbons in surface soil in Tianjin, China

Principal component analysis and multiple linear regression were applied to apportion sources of polycyclic aromatic hydrocarbons (PAHs) in surface soils of Tianjin, China based on the measured PAH concentrations of 188 surface soil samples. Four principal components were identified representing coal combustion, petroleum, coke oven plus biomass burning, and chemical industry discharge, respectively. The contributions of major sources were quantified as 41% from coal, 20% from petroleum, and 39% from coking and biomass, which are compatible with PAH emissions estimated based on fuel consumption and emission factors. When the study area was divided into three zones with distinctive differences in soil PAH concentration and profile, different source features were unveiled. For the industrialized Tanggu-Hangu zone, the major contributors were cooking (43%), coal (37%) and vehicle exhaust (20%). In rural area, however, in addition to the three main sources, biomass burning was also important (13%). In urban-suburban zone, incineration accounted for one fourth of the total.     

Atmospheric trace metal pollution in the Naples urban area based on results from moss and lichen bags

The results of trace element content analysed in Sphagnum capillifolium and Pseudevernia furfuracea exposed in bags in 1999 are reconsidered to evaluate the reliability of moss and lichen transplants to detect urban trace element atmospheric pollution, using Naples as a case example. After 4 months' exposure, trace element concentrations were at least twice as high as the pre-exposure values and in general higher in Sphagnum than in Pseudevernia. Moss samples were enriched in the following order: As=Cu>Mo>Pb>V>Co>Cr>Zn; lichen samples in the order: Mo>Cu>As=Co=Ni>V>Pb. Based on the calculation of a cumulative load factor, all sites located along the coast had higher trace element loads compared to sites in the hilly inland area. Complementary SEM, TEM and EDS observations showed, despite significant damage to tissue and cell integrity, the recurrent presence of particulate matter in moss and lichen, indicating the considerable presence of dust in the urban atmosphere which, according to chemical composition, may be due both to anthropogenic and natural sources such as volcanic rock and soil and sea salts.