The stable carbon isotope composition of PM2.5 and PM10 in Mexico City Metropolitan Area air

The sources and distribution of carbon in ambient suspended particles (PM_2.5 and PM₁₀) of Mexico City Metropolitan Area (MCMA) air were traced using stable carbon isotopes (¹³C/¹²C). Tested potential sources included rural and agricultural soils, gasoline and diesel, liquefied-petroleum gas, volcanic ash, and street dust. The complete combustion of LP gas, diesel and gasoline yielded the lightest δ¹³C values (?27 to ?29‰ vs. PDB), while street dust (PM₁₀) represented the isotopically heaviest endmember (?17‰). The δ¹³C values of rural soils from four geographically separated sites were similar (?20.7 ± 1.5‰). δ¹³C values of particles and soot from diesel and gasoline vehicle emissions and agricultural soils varied between ?23 and ?26‰. Ambient PM samples collected in November of 2000, and March and December of 2001 at three representative receptor sites of industrial, commercial and residential activities had a δ¹³C value centered around ?25.1‰ in both fractions, resulting from common carbon sources. The predominant carbon sources to MCMA atmospheric particles were hydrocarbon combustion (diesel and/or gasoline) and particles of geological origin. The significantly depleted δ¹³C values from the industrial site reflect the input of diesel combustion by mobile and point source emissions. Based on stable carbon isotope mass balance, the carbon contribution of geological sources at the commercial and residential sites was approximately 73% for the PM₁₀ fraction and 54% for PM_2.5. Although not measured in this study, biomass-burning emissions from nearby forests are an important carbon source characterized by isotopically lighter values (?29‰), and can become a significant contributor (67%) of particulate carbon to MCMA air under the prevalence of southwesterly winds. Alternative sources of these ¹³C-depleted particles, such as cooking fires and municipal waste incineration, need to be assessed. Results show that stable carbon isotope measurements are useful for distinguishing between some carbon sources in suspended particles to MCMA air, and that wind direction has an impact on the distribution of carbon sources in this basin.     

混凝-生物接触氧化处理合成橡胶碱洗废水

对化学合成橡胶碱洗废水进行了有机组分和可生化性分析,废水主要含有氯甲烷、六甲苯、异丁醇、甲醇等污染物质,生化降解实验中废水TOC可在6 d内从60.9 mg/L下降至0.0 mg/L,可生化降解性好,适于生化处理。选择混凝-生物接触氧化组合工艺对废水进行处理,采用优化条件(pH=8、PAC=40 mg/L、PAM=8 mg/L)进行混凝,碱洗废水COD去除率为9.95%~72.94%(平均31.51%);混凝后的碱洗废水与冲洗废水1∶5混合进行接触氧化处理,在HRT为36 h的情况下,COD去除率为65.6%~72.6%(平均70.4%),出水COD为134~331 mg/L,满足企业废水排放市政管网的要求;同时,实验发现COD去除率与COD容积负荷存在指数函数变化关系。     

Nitrogen limited biobarriers remove atrazine from contaminated water: laboratory studies

Atrazine is one of the most frequently used herbicides. This usage coupled with its mobility and recalcitrant nature in deeper soils and aquifers makes it a frequently encountered groundwater contaminant. We formed biobarriers in sand filled columns by coating the sand with soybean oil; after which, we inoculated the barriers with a consortium of atrazine-degrading microorganisms and evaluated the ability of the barriers to remove atrazine from a simulated groundwater containing 1 mg L(-1) atrazine. The soybean oil provided a carbon rich and nitrogen poor substrate to the microbial consortium. Under these nitrogen-limiting conditions it was hypothesized that bacteria capable of using atrazine as a source of nitrogen would remove atrazine from the flowing water. Our hypothesis proved correct and the biobarriers were effective at removing atrazine when the nitrogen content of the influent water was low. Levels of atrazine in the biobarrier effluents declined with time and by the 24th week of the study no detectable atrazine was present (limit of detection<0.005 mg L(-1)). Larger amounts of atrazine were also removed by the biobarriers; when biobarriers were fed 16.3 mg L(-1) atrazine 97% was degraded. When nitrate (5 mg L(-1) N), an alternate source of nitrogen, was added to the influent water the atrazine removal efficiency of the barriers was reduced by almost 60%. This result supports the hypothesis that atrazine was degraded as a source of nitrogen. Poisoning of the biobarriers with mercury chloride resulted in an immediate and large increase in the amount of atrazine in the barrier effluents confirming that biological activity and not abiotic factors were responsible for most of the atrazine degradation. The presence of hydroxyatrazine in the barrier effluents indicated that dehalogenation was one of the pathways of atrazine degradation. Permeable barriers might be formed in-situ by the injection of innocuous vegetable oil emulsions into an aquifer or sandy soil and used to remove atrazine from a contaminated groundwater or to protect groundwater from an atrazine spill.     

Levels of PCDD/F in adipose tissue on non-occupationally exposed subjects living near a hazardous waste incinerator in Catalonia, Spain

The potential adverse effects on human health of hazardous waste incinerators (HWIs) are a subject of concern. The construction of the first and till now only HWI in Spain finished in 1999. In 2007, after approximately 9 years of regular operations in the facility, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined by HRGC/HRMS in samples of adipose tissue of 15 autopsied subjects living in the area under potential impact of the HWI (Constantí, Tarragona County, Catalonia). These data were compared with the levels found in two previous surveys performed in 1998 (baseline) and 2002. The current mean PCDD/F concentration in adipose tissue was 14.6 pg WHO-TEQ/g of fat (range: 3.3–55.4 pg WHO-TEQ/g of fat). It means significant changes (a reduction of 64% and an increase of 47%) in the mean PCDD/F levels in comparison to those found in 1998 and 2002: 40.1 and 9.9 pg WHO-TEQ/g of fat, respectively. Women showed higher levels of PCDD/F than men (23.8 vs 11.2 pg WHO-TEQ/g of fat). The increase in the last 5 years would not be directly attributable to exposure to PCDD/F emitted by the HWI, as other biological monitors such as human plasma and milk decreased during the same period.     

Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

The effects of scale and spatial heterogeneities on diffusion in volcanic breccias and basalts: Amchitka Island, Alaska

Knowledge of the factors that influence the diffusion of contaminants, such as the diffusivity and the connected porosity, is crucial to modeling the long-term fate and transport of contaminants in subsurface systems with small or negligible advective flow, such as in fractured crystalline rock. Fractured rock is naturally heterogeneous, and hence, understanding the diffusivity of a molecule through this material (or the formation factor of the medium) becomes a complex problem, with critical concerns about the scale of laboratory measurements and about the spatial variability of these measurements relative to the scale needed for fate and transport modeling. This study employed both electrical and tracer-based laboratory methods to investigate the effects of scale and pore system connectivity on the diffusivity for volcanic matrix rock derived from the study site, a former underground nuclear test site at Amchitka Island, Alaska. The results of these investigations indicate a relatively well-connected pore system with scale effects generally limited to approximately 6 cm lengths and well-correlated to observed heterogeneous features. An important conclusion resulting from this study, however, is that there is a potential for the estimated diffusivity to be misrepresented by an order of magnitude if multiple samples or longer sample lengths are not used. Given the relatively large number of measurements resulting from these investigations, an analysis of the probability density function (PDF) of the diffusivity was possible. The PDF of the diffusivity was shown to generally follow a normal distribution for individual geologic layers. However, when all of the geologic layers are considered together, the distribution of the subsurface as a whole was shown to follow a lognormal distribution due to the order of magnitude differences amongst the layers. An understanding of these distributions is essential for future stochastic modeling efforts.     

A detailed field-based evaluation of naphthenic acid mobility in groundwater

An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO₃, Na, Cl, SO₄, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L^− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization.     

Characterization of silver release from commercially available functional (nano)textiles

Silver, both in the nano as well as in other forms, is used in many applications including antimicrobial textiles. Washing of such textiles has already been identified as an important process that results in the release of silver into wastewater. This study thus investigated the release of silver from eight different commercially available silver-textiles during a washing and rinsing cycle. The silver released was size-fractionated and characterized using electron microscopy. In addition, the antimicrobial functionality of the textiles was tested before and after washing. Three of the textiles contained nanosized silver (labeled or confirmed by manufacturers’ information), another used a metallic silver wire and four contained silver in undeclared form. The initial silver content of the textiles was between 1.5 and 2925 mg Ag/kg. Only four of the investigated textiles leached detectable amounts of silver, of which 34-80% was in the form of particles larger than 450 nm. Microscopic analysis of the particles released in the washing solutions identified Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large AgCl particles, nanosilver sulfide and metallic nano-Ag, respectively. The nanoparticles were mainly found in highly agglomerated form. The identified nanotextiles showed the highest antimicrobial activity, whereas some of the other textiles, e.g. the one with a silver wire and the one with the lowest silver content, did not reduce the growth of bacteria at all. The results show that different silver textiles release different forms of silver during washing and that among the textiles investigated AgCl was the most frequently observed chemical form in the washwater.     

Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC = 0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC = 0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.     

Use of a food web model to evaluate the factors responsible for high PCB fish concentrations in Lake Ellasjøen, a high Arctic Lake

Background, aim, and scope

Lake Ellasjøen, located in the Norwegian high arctic, contains the highest concentrations of polychlorinated biphenyls (PCBs) ever recorded in fish and sediment from high arctic lakes, and concentrations are more than 10 times greater than in nearby Lake Øyangen. These elevated concentrations in Ellasjøen have been previously attributed, in part, to contaminant loadings from seabirds that use Ellasjøen, but not Øyangen, as a resting area. However, other factors, such as food web structure, organism growth rate, weight, lipid content, lake morphology, and nutrient inputs from the seabird guano, also differ between the two systems. The aim of this study is to evaluate the relative influence of these factors as explanatory variables for the higher PCB fish concentrations in Ellasjøen compared with Øyangen, using both a food web model and empirical data.

Methods

The model is based on previously developed models but parameterized for Lakes Ellasjøen and Øyangen using measured data wherever possible. The model was applied to five representative PCB congeners (PCB 105, 118, 138, 153, and 180) using measured sediment and water concentrations as input data and evaluated with previously collected food web data.

Results

Modeled concentrations are within a factor of two of measured concentrations in 60% and 40% of the cases in Lakes Ellasjøen and Øyangen, respectively, and within a factor of 10 in 100% of the cases in both lakes. In many cases, this is comparable to the variability associated with the data as well as the efficacy of the predictions of other food web model applications.

Discussion

We next used the model to quantify the relative importance of five major differences between Ellasjøen and Øyangen by replacing variables representing each of these factors in the Ellasjøen model with those from Øyangen, in separate simulations. The model predicts that the elevated PCB concentrations in Ellasjøen water and sediment account for 49%–58% of differences in modeled fish PCB concentrations between lakes. These elevated sediment and, to a lesser extent, water concentrations in Ellasjøen are due to PCB loadings from seabird guano. However, sediment–water fugacity ratios of PCBs are consistently greater in Ellasjøen compared with Øyangen, which suggests that internal lake processes also contribute to differences in sediment and water concentrations. We hypothesize that the nutrients associated with guano influence sediment–water fugacity ratios of PCBs by increasing the stock of pelagic algae. As both these algae and the guano settle, their organic carbon content is degraded faster than PCBs, which causes an extra magnification step in Ellasjøen before these detrital particles are consumed by benthic organisms, which are in turn consumed by fish. The model predicts that the remaining ～50% of the differences in PCB concentrations observed between the fish of these lakes are due to other subtle differences in their food web structures.

Conclusions

In conclusion, based on the results of a food web model, we found that the most dominant factors influencing the higher PCB fish concentrations in Lake Ellasjøen compared with Øyangen are the higher sediment and water concentrations in Ellasjøen, caused by seabird guano. Together, sediment and water are predicted to account for 49%–58% of differences in fish concentrations between lakes. Although seabird guano provides a source of nutrients to the lake, in addition to contaminants, empirical data and indirect model results suggest that nutrients are not leading to decreased bioaccumulation, in contrast to what has been observed in temperate, pelagic food webs.

Recommendations and perspectives

The results of this study emphasize the importance of considering even small differences in food web structure when comparing bioaccumulation in two lakes; although the food web structures of Ellasjøen and Øyangen differ only slightly, the model predicts that these differences account for most of the remaining ～50% of the differences in PCB fish concentrations between the two lakes. This study further demonstrates the utility of food web models as we were able to predict and tease apart the influence of various factors responsible for the elevated concentrations in the fish from Lake Ellasjøen, which would have been difficult using the field data alone.