Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/z 44. Despite differences for three projects with ratios of m/z 44 to m/z 57 fragments less than 10, five projects showed a linear trend between the project-average m/z 44 to m/z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/z 44 as a carboxylic acid group marker and m/z 57 as an alkane group marker.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.     

Metal stress and decreased tree growth in response to biosolids application in greenhouse seedlings and in situ Douglas-fir stands

To assess physiological impacts of biosolids on trees, metal contaminants and phytochelatins were measured in Douglas-fir stands amended with biosolids in 1982. A subsequent greenhouse study compared these same soils to soils amended with fresh wastewater treatment plant biosolids. Biosolids-amended field soils had significantly higher organic matter, lower pH, and elevated metals even after 25 years. In the field study, no beneficial growth effects were detected in biosolids-amended stands and in the greenhouse study both fresh and historic biosolids amendments resulted in lower seedling growth rates. Phytochelatins - bioindicators of intracellular metal stress - were elevated in foliage of biosolids-amended stands, and significantly higher in roots of seedlings grown with fresh biosolids. These results demonstrate that biosolids amendments have short- and long-term negative effects that may counteract the expected tree growth benefits.     

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg_d), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg_d to DOC (r² = 0.87), but progressively stronger correlations of THg_d with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV₂₅₄ absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THg_d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg_d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg_d flux in drainage waters.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Microbial reduction of sulfate injected to gas condensate plumes in cold groundwater

Despite a rapid expansion over the past decade in the reliance on intrinsic bioremediation to remediate petroleum hydrocarbon plumes in groundwater, significant research gaps remain. Although it has been demonstrated that bacterial sulfate reduction can be a key electron accepting process in many petroleum plumes, little is known about the rate of this reduction process in plumes derived from crude oil and gas condensates at cold-climate sites (mean temperature <10 degrees C), and in complex hydrogeological settings such as silt/clay aquitards. In this field study, sulfate was injected into groundwater contaminated by gas condensate plumes at two petroleum sites in Alberta, Canada to enhance in-situ bioremediation. In both cases the groundwater near the water table had low temperature (6-9 degrees C). Monitoring data had provided strong evidence that bacterial sulfate reduction was a key terminal electron accepting process (TEAP) in the natural attenuation of dissolved hydrocarbons at these sites. At each site, water with approximately 2000 mg/L sulfate and a bromide tracer was injected into a low-sulfate zone within a condensate-contaminant plume. Monitoring data collected over several months yielded conservative estimates for sulfate reduction rates based on zero-order kinetics (4-6 mg/L per day) or first-order kinetics (0.003 and 0.01 day(-1)). These results favor the applicability of in-situ bioremediation techniques in this region, under natural conditions or with enhancement via sulfate injection.     

Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Persistent organic pollutants in 9/11 world trade center rescue workers: reduction following detoxification

Exposure to toxins following the September 11, 2001 attack on and collapse of the World Trade Center (WTC) is of particular concern given the ultra fine particulate dust cloud, high temperature combustion, and months-long fire. Firefighters, paramedics, police and sanitation crews are among the approximately 40000 personnel who labored for weeks and months on rescue and cleanup efforts. Many of the rescue workers have subsequently developed symptoms that remain unresolved with time. This study characterizes body burdens of polychlorinated biphenyls (PCBs), polychlorinated dibenzofurans (PCDFs), and polychlorinated dioxins (PCDDs) in rescue workers and citizens exposed following the WTC collapse. Our research includes a pilot evaluation of a detoxification method aimed at reducing toxic burden. Many congeners were found at elevated levels, in ranges associated with occupational exposures. Post-detoxification testing revealed reductions in these congeners and despite the small study size, some reductions were statistically significant. Health symptoms completely resolved or were satisfactorily improved on completion of treatment. These results argue for a larger treatment study of this method and an overall treatment approach to address toxic burden.     

Effect of sequencing batch reactor operation on presence and concentration of tetracycline-resistant organisms.

The effect of sequencing batch reactor operation on presence and concentration of tetracycline-resistant organisms was studied as a function of organic loading rate (OLR) and solids retention time (SRT), with and without supplemented influent tetracycline. These effects were evaluated using bacterial counts, bacterial production, system growth rate, and percent resistance. These evaluation parameters were applied to both intermediate resistant and resistant heterotrophs, enterics, and lactose fermenters. Tetracycline intermediate resistant and resistant bacteria are defined as the survival of colonies on agar with 5 and 20 mg/L tetracycline, respectively. Based on these studies, increases in influent tetracycline concentration and OLR resulted in amplification of tetracycline resistance. Decreases in SRT also resulted in amplification of tetracycline resistance.