Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.     

Modeling pesticide fate in a small tidal estuary

The exposure analysis modeling system (EXAMS), a pesticide fate model developed by the U.S. Environmental Protection Agency, was modified to model the fate of the herbicides atrazine and metolachlor in a small tidally dominated estuary (Bath Creek) in North Carolina, USA where freshwater inflow accounts for only 3% of the total flow. The modifications simulated the changes that occur during the tidal cycle in the estuary, scenarios that are not possible with the original EXAMS model. Two models were created within EXAMS, a steady-state model and a time-variant tidally driven model. The steady-state model accounted for tidal flushing by simply altering freshwater input to yield an estuary residence time equal to that measured in Bath Creek. The tidal EXAMS model explicitly incorporated tidal flushing by modifying the EXAMS code to allow for temporal changes in estuary physical attributes (e.g., volume). The models were validated with empirical measurements of atrazine and metolachlor concentrations in the estuary shortly after herbicide application in nearby fields and immediately following a rain event. Both models provided excellent agreement with measured concentrations. The steady-state EXAMS model accurately predicted atrazine concentrations in the middle of the estuary over the first 3 days and under-predicted metolachlor by a factor of 2–3. The time-variant, tidally driven EXAMS model accurately predicted the rise and plateau of both herbicides over the 6-day measurement period. We have demonstrated the ability of these modified EXAMS models to be useful in predicting pesticide fate and exposure in small tidal estuaries. This is a significant improvement and expansion of the application of EXAMS, and given the wide use of EXAMS for surface water quality modeling by both researchers and regulators and the ability of EXAMS to interface with terrestrial models (e.g., pesticide root zone model) and bioaccumulation models, we now have an easily-accessible and widely accepted means of modeling chemical fate in estuaries.     

Metal contents of marine turtle eggs (Chelonia mydas; Lepidochelys olivacea) from the tropical eastern pacific and the implications for human health

Concentrations of eight elements were measured in Chelonia mydas and Lepidochelys olivacea eggs collected along the Pacific coast of Panama. Manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd), and mercury (Hg) concentrations were similar to previous reports of these species from around the world, while lead (Pb) was lower than previous reports. Cd posed the highest health risk to people who regularly eat the eggs, with average consumption rates leading to target hazard quotients (THQ) of up to 0.35 ± 0.15. Our conclusions indicate that current turtle egg consumption in isolated, coastal Pacific communities may pose a health concern for young children, and that youth and young adults should limit their consumption of turtle eggs to reduce their total intake of nonessential metals.     

High time-resolved measurements of organic air toxics in different source regimes

High time-resolved (HTR) measurements can provide significant insight into sources and exposures of air pollution. In this study, an automated instrument was developed and deployed to measure hourly concentrations of 18 gas-phase organic air toxics and 6 volatile organic compounds (VOCs) at three sites in and around Pittsburgh, Pennsylvania. The sites represent different source regimes: a site with substantial mobile-source emissions; a residential site adjacent to a heavily industrialized zone; and an urban background site. Despite the close proximity of the sites (less than 13 km apart), the temporal characteristic of outdoor concentrations varied widely. Most of the compounds measured were characterized by short periods of elevated concentrations or plume events, but the duration, magnitude and composition of these events varied from site to site. The HTR data underscored the strong role of emissions from local sources on exposure to most air toxics. Plume events contributed more than 50% of the study average concentrations for all pollutants except chloroform, 1,2-dichloroethane, and carbon tetrachloride. Wind directional dependence of air toxic concentrations revealed that emissions from large industrial facilities affected concentrations at all of the sites. Diurnal patterns and weekend/weekday variations indicated the effects of the mixing layer, point source emissions patterns, and mobile source air toxics (MSATs) on concentrations. Concentrations of many air toxics were temporally correlated, especially MSATs, indicating that they are likely co-emitted. It was also shown that correlations of the HTR data were greater than lower time resolution data (24-h measurements). This difference was most pronounced for the chlorinated pollutants. The stronger correlations in HTR measurements underscore their value for source apportionment studies.     

Isoprene emissions and climate

Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and the carbon cycle. Isoprene is quantitatively the most important of the non-methane BVOCs (NMBVOCs), with an annual emission of about 400–600 TgC; about 90% of this is emitted by terrestrial plants. Incorporating a mechanistic treatment of isoprene emissions within land-surface schemes has recently become a focus for the modelling community, the aim being to quantify the potential magnitude of associated climate feedbacks. However, these efforts are hampered by major uncertainties about why plants emit isoprene and the relative importance of different environmental controls on isoprene emission. The availability and reliability of observations of isoprene fluxes from different types of vegetation is limited, and this also imposes constraints on model development. Nevertheless, progress is being made towards the development of mechanistic models of isoprene emission which, in conjunction with atmospheric chemistry models, will ultimately allow improved quantification of the feedbacks between the terrestrial biosphere and climate under past and future climate states.     

Origin of major ions in monthly rainfall events at the Bamenda Highlands, North West Cameroon

Rainwater characteristics can reveal emissions from various anthropogenic and natural sources into the atmosphere. The physico-chemical characteristics of 44 monthly rainfall events （collected between January and December 2012） from 4 weather stations （Bamenda, Ndop plain, Ndawara and Kumbo） in the Bamenda Highlands （BH） were investigated. The purpose was to determine the sources of chemical species, their seasonal inputs and suitability of the rainwater for drinking. The mean pH of 5 indicated the slightly acidic nature of the rainwater. Average total dissolved solids （TDS） were low （6.7 mg/L）, characteristic of unpolluted atmospheric moisture/air. Major ion concentrations （mg/L） were low and in the order K＋ 〉 Ca2＋ 〉 Mg2~ 〉 Na＋ for cations and NO3 〉〉 HCO3 〉 SO] 〉 CI- 〉 PO3- 〉 F- for anions. The average rainwater in the area was mixed Ca-Mg-SO4-CI water type. The CI-/Na＋ ratio （1.04） was comparable to that of seawater （1.16）, an indication that N a＋ and CI originated mainly from marine （Atlantic Ocean） aerosols. High enrichments of Ca2＋, Mg2＋ and SO2- to Na＋ ratios relative to seawater ratios （constituting 44% of the total ions） demonstrated their terrigenous origin, mainly from Saharan and Sahelian arid dusts. The K＋/Na＋ ratio （2.24）, which was similar to tropical vegetation ash （2.38）, and NO3 was essentially from biomass burning. Light （〈 100 mm） pre-monsoon and post-monsoon convective rains were enriched in major ions than the heavy （〉 100 mm） monsoon rains, indicating a high contribution of major ions during the low convective showers. Despite the acidic nature, the TDS and major ion concentrations classified the rainwater as potable based on the WHO guidelines.     

Direct evidence of trophic interactions among apex predators in the Late Triassic of western North America

Hypotheses of feeding behaviors and community structure are testable with rare direct evidence of trophic interactions in the fossil record (e.g., bite marks). We present evidence of four predation, scavenging, and/or interspecific fighting events involving two large paracrocodylomorphs (=‘rauisuchians’) from the Upper Triassic Chinle Formation (～220–210 Ma). The larger femur preserves a rare history of interactions with multiple actors prior to and after death of this ～8–9-m individual. A large embedded tooth crown and punctures, all of which display reaction tissue formed through healing, record evidence of a failed attack on this individual. The second paracrocodylomorph femur exhibits four unhealed bite marks, indicating the animal either did not survive the attack or was scavenged soon after death. The combination of character states observed (e.g., morphology of the embedded tooth, ‘D’-shaped punctures, evidence of bicarination of the marking teeth, spacing of potentially serial marks) indicates that large phytosaurs were actors in both cases. Our analysis of these specimens demonstrates phytosaurs targeted large paracrocodylomorphs in these Late Triassic ecosystems. Previous distinctions between ‘aquatic’ and ‘terrestrial’ Late Triassic trophic structures were overly simplistic and built upon mistaken paleoecological assumptions; we show they were intimately connected at the highest trophic levels. Our data also support that size cannot be the sole factor in determining trophic status. Furthermore, these marks provide an opportunity to start exploring the seemingly unbalanced terrestrial ecosystems from the Late Triassic of North America, in which large carnivores far outnumber herbivores in terms of both abundance and diversity.     

北京典型道路交通环境机动车黑碳排放与浓度特征研究

本研究对2009年北京市典型道路(北四环中路西段)进行实际交通流监测和调研,分析了总车流量、车型构成和平均速度的日变化规律.应用北京机动车排放因子模型(EMBEV模型)和颗粒物黑碳排放的研究数据,计算该路段的黑碳平均排放因子和排放强度.根据同期观测的气象数据,应用AERMOD模型对道路黑碳排放进行了扩散模拟,并根据城市背景站点和道路边站点的监测数据对模拟结果进行了验证.研究表明,该路段黑碳平均排放因子与重型柴油车在总车流中所占比例呈现出极强的相关性,由于北京市实行货车区域限行制度,日间时段总车流的平均黑碳排放因子为(9.3±1.2)mg·km-1·veh-1,而夜间时段上升至(29.5±11.1)mg·km-1·veh-1.全天时均黑碳排放强度为17.9~115.3g·km-1·h-1,其中早(7:00—9:00)晚(17:00—19:00)高峰时段的黑碳排放强度分别为(106.1±13.0)g·km-1·h-1和(102.6±6.2)g·km-1·h-1.基于同期监测数据验证,AERMOD模型的模拟效果较好.模拟时段的道路黑碳排放对道路边监测点的平均浓度贡献为(2.8±3.5)μg·m-3.由于局地气象条件差异,日间和夜间的机动车排放对道路边黑碳的模拟浓度存在显著差异.日间时段,小型客车排放对道路边站点的黑碳浓度贡献最高,达(1.07±1.57)μg·m-3;其次为公交车,达(0.58±0.85)μg·m-3.夜间时段货车比例明显上升,其黑碳排放占主导地位,贡献浓度(2.44±2.31)μg·m-3.     

Modeling linkages between sediment resuspension and water quality in a shallow,eutrophic, wind-exposed lake

The interactions between bed sediments and the water column in shallow, eutrophic lakes have tremendous implications for the fate and transport of nutrients in those water bodies. This has resulted in the development of water quality models for lakes incorporating the processes of sediment resuspension. Reliable resuspension models are thus needed to accurately represent this phenomenon. In this paper, three different sediment-resuspension models are combined with a hydrodynamic and water quality model, dynamic lake model-water quality (DLM-WQ), and the resulting models are used to simulate nutrient distributions in the highly eutrophic Salton Sea, California, USA. One of the resuspension formulas is based upon sediment characteristics as well as the bed shear stress exerted by wind-induced waves and currents, while the other two are standard, power-law-type formulas for cohesive sediments with two different exponents. The outputs for water quality variables, such as temperature, chlorophyll a, dissolved oxygen and nutrients, obtained from the three resulting models and from an earlier DLM-WQ run with a simple empirical sediment-resuspension model are compared with measured data. The level of agreement between the simulations and the measured data is assessed by using both statistical and graphical model evaluation methods, including measures of residual errors, sample autocorrelations, t-tests, and box plots. Based on these assessments, DLM-WQ with an extended version of the García and Parker [García, M.H., Parker, G., 1993. Experiments on the entrainment of sediment into suspension by a dense bottom current. J. Geophys. Res.-Oceans 98, 4793–4807] relationship gave the best results for water quality in the Salton Sea, confirming that the use of formulas with more information on the sediment characteristics yields more accurate results. To the best of our knowledge, this is the first effort to combine water quality models for lakes and reservoirs with a sediment-resuspension model which was originally intended for open-channel flows. The simulations confirm that sediment resuspension is the most dominant process in the Salton Sea's nutrient cycling. The effect of proposed physical changes to the Salton Sea on water quality characteristics is also addressed.