Atmospheric Hexachlorocyclohexanes in the North Pacific Ocean and the adjacent Arctic region: spatial patterns, chiral signatures, and sea-air exchanges

During the 2003 Chinese Arctic Research Expedition (CHINARE2003) from the Bohai Sea to the high Arctic (37 degrees N to 80 degrees N) aboard the icebreaker Xuelong (Snow Dragon), air samples were collected for the analysis of hexachlorocyclohexanes (HCHs) in the North Pacific Ocean and adjacent Arctic region. The sigma HCHs (alpha-HCH + gamma-HCH) ranged from 2.3 to 95.1 pg/m3 with the highest levels observed in Far East Asia (32.5 pg/m3), followed by the North Pacific Ocean (17.0 pg/m3) and the Arctic (7.3 pg/ m3). Compared to previous studies in the same areas in 1990s, our measurements were approximately 1 order of magnitude lower. Because of disproportionate chemical reduction and physical fractioning during long-range transport, the ratios of alpha-HCH to gamma-HCH (alpha/gamma-HCH) showed a significant increasing trend from low to high latitudes, suggesting thatthe alpha/gamma-HCH range of 4-7 could not be used to identify sources of technical HCHs especially in remote areas. The ratios of (+)-alpha-HCH to the sum of (+)-alpha-HCH and (-)-alpha-HCH were on average much more biased from 0.5 compared to previous observations in mid-1990s, indicating the exchange of atmospheric alpha-HCH with those in the oceans, where (+)-alpha-HCH was selectively depleted in biological degradation processes. Estimated fugacity ratios based on available data for both alpha-HCH and gamma-HCH further implied their net volatilization from seawater to air in the Arctic Ocean.     

Levoglucosan and other cellulose markers in pyrolysates of Miocene lignites: geochemical and environmental implications

Using the pyrolysis-gas chromatography-mass spectrometry and off-line pyrolysis/silylation methods for lignites from three Miocene brown coal basins of Poland resulted in the characterization of many organic compounds, including dominant cellulose degradation products such as levoglucosan, 1,6-anhydro-beta-D-glucofuranose, and 1,4:3,6-dianhydroglucopyranose. Levoglucosan is a general source-specific tracer for wood smoke in the atmosphere and recent sediments. The presence of unusually high levels of this compound in brown coal pyrolysates suggests that a portion of this compound concentration in some airsheds may originate from lignite combustion. On the other hand, nonglucose anhydrosaccharides, in particular, mannosan and galactosan, typical of hemicellulose, are not detected in those lignite pyrolysates investigated. This indicates that mannosan and galactosan are better specific tracers for combustion of contemporary biomass in those regions were the utilization of brown coals containing fossilized cellulose is important.     

Assessing TMDL effectiveness using flow-adjusted concentrations: a case study of the Neuse River,North Carolina

Integrated control of both point and nonpoint source water pollution using Total Maximum Daily Load (TMDL) assignments will be a major regulatory focus over the next decade. We propose the use of "flow-adjusted" pollutant concentrations to evaluate the effectiveness of management actions taken to meet approved TMDLs. Pollutant concentrations are usually highly correlated with streamflow, and flow is strongly weather-dependent. Thus, pollutant loads, which are calculated as pollutant concentration multiplied by streamflow, have a large weather-dependent variance component. This natural variation can be removed by calculating flow-adjusted concentrations. While such values are not a direct measure of pollutant load, they make it easier to discern changes in streamwater quality. Additionally, they are likely to be a better predictor of pollutant concentrations in the receiving waterbody. We demonstrate the use of this technique using long-term nutrient data from the Neuse River in North Carolina. The Neuse River Estuary has suffered many eutrophication symptoms, and a program to reduce nutrient loading has been in place for several years. We show that, in addition to revealing recent reductions in nutrient inputs, annual flow-adjusted riverine nutrient concentrations show a more pronounced relationship with estuarine nutrient concentrations than do annual nutrient loads. Thus, we suggest that the calculation of flow-adjusted concentrations is a useful technique to aid in assessment of TMDL implementation.     

Polychlorinated biphenyls in nonaccumulating, century-old sediments: sources, signatures, and mechanism of introduction

This study documents the occurrence of highly chlorinated PCB congeners in stream sediment deposited over 100 years ago. Penta- to heptachlorinated congeners (> 80%) have been found at concentrations up to 78.8 ng/g (dw) in core samples of a small, rural tributary of Lake Ontario. Lower chlorinated congeners and other organochlorine compounds occur sporadically; 210Pb and 137Cs are lacking. The most plausible mechanism is accumulation of dissolved-phase PCBs in permeable sediments adjacent to the creek channel. The similarity between core and air samples collected in the drainage basin suggests derivation from a residual fraction of atmospherically derived PCB congeners.     

Thioarsenates in geothermal waters of Yellowstone National Park: determination, preservation, and geochemical importance

Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chromatography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCI addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed immediately. Thioarsenates occurred over a pH range of 2.1 to 9.3 in the geothermal waters. They clearly predominated under alkaline conditions (up to 83% of total arsenic), but monothioarsenate also was detected in acidic waters (up to 34%). Kinetic studies along a drainage channel showed the importance of thioarsenates for the fate of arsenic discharged from the sulfidic hot spring. The observed arsenic speciation changes suggest three separate reactions: the transformation of trithioarsenate to arsenite (major initial reaction), the stepwise ligand exchange from tri- via di- and monothioarsenate to arsenate (minor reaction), and the oxidation of arsenite to arsenate, which only becomes quantitatively important after thioarsenates have disappeared.     

DDE in sediments of the Palos Verdes Shelf, California: in situ transformation rates and geochemical fate

From 1947 to 1971 the world's largest manufacturer of DDT discharged process wastes into the sewers of Los Angeles County. Roughly 870-1450 t of DDT were released to the ocean off Palos Verdes, CA, a portion of which (approximately 100 t) resides in sediments on the continental shelf and slope. The most abundant DDT compound in the sediments, p,p'-DDE, is degrading by reductive dechlorination, but the rate of transformation and factors controlling it are not well understood. In order to estimate in situ transformation rates and predict the long-term fate of p,p'-DDE, box cores were collected in 1992 and 2003 from a single location on the Palos Verdes Shelf and analyzed for 8 DDT compounds and 84 polychlorinated biphenyl (PCB) congeners. The PCBs show no evidence of dechlorination, and inventories did not change between 1992 and 2003. By contrast, the inventory of p,p'-DDE decreased by 43%, whereas that of p,p'-DDMU, the putative reductive dechlorination product, increased by 34%. The first-order transformation rate for p,p'-DDE at the study site is 0.051 +/- 0.006 yr(-1). A multistep reaction model suggests that inventories of p,p'-DDE and p,p'-DDMU will continue to decline, whereas that of p,p'-DDNU will reach a maximum around 2014.     

Estimating potential environmental loadings of Cryptosporidium spp. and Campylobacter spp. from livestock in the Grand River Watershed, Ontario, Canada

Exposure to waterborne pathogens in recreational or drinking water is a serious public health concern. Thus, it is important to determine the sources of pathogens in a watershed and to quantify their environmental loadings. The natural variability of potentially pathogenic microorganisms in the environment from anthropogenic, natural, and livestock sources is large and has been difficult to quantify. A first step in characterizing the risk of nonpoint source contamination from pathogens of livestock origin is to determine the potential environmental loading based on animal prevalence and fecal shedding intensity. This study developed a probabilistic model for estimating the production of Cryptosporidium spp. and Campylobacter spp. from livestock sources within a watershed. Probability density functions representing daily pathogen production rates from livestock were simulated for the Grand River Watershed in southwestern Ontario. The prevalence of pathogenic microorganisms in animals was modeled as a mixture of beta-distributions with parameters drawn from published studies. Similarly, gamma-distributions were generated to describe animal pathogen shedding intensity. Results demonstrate that although cattle are responsible for the largest amount of manure produced, other domesticated farm animals contribute large numbers of the two pathogenic microorganisms studied. Daily pathogen production rates are highly sensitive to the parameters of the gamma-distributions, illustrating the need for reliable data on animal shedding intensity. The methodology may be used for identifying source terms for pathogen fate and transport modeling and for defining and targeting regions that are most vulnerable to water contamination from pathogenic sources.     

Oviposition of Dermestes maculatus DeGeer,the hide beetle,as affected by biological and environmental conditions

Experiments were conducted to document the oviposition behaviors and preferences of the female hide beetle, Dermestes maculatus DeGeer, in order to optimize the collection of eggs and neonate larvae for biological assays. Factors evaluated were the type of oviposition substrate, preference for and type of preconditioned diet, sex ratio and light/dark conditions. We determined that synthetic fur was a suitable medium for oviposition and collecting progeny. Fur type and position were not important factors in oviposition preference (average progeny production ranged from 27.9 ± 6.4 to 42.4 ± 6.4); however, the use of paper as a cover and no cover treatments were statistically different from the fur treatments and resulted in average progeny productions of 5.2 ± 1.1 and 3.4 ± 0.7, respectively. Diet preconditioned by the colony was a statistically significant (P < 0.001) factor for oviposition preference, compared with unconditioned diet, and inhibited oviposition. The type of preconditioning was also an important factor (P = 0.004); we examined four treatments: no conditioning, conditioning by larvae, conditioning by adult males and conditioning by adult females. The mean progeny production for the control (no conditioning) was 52.9 ± 13.6, which was not significantly different from the larval conditioning treatment (48.1 ± 5.9). Both adult conditioned treatments were statistically different for progeny production, adult male (22.3 ± 2.9) and adult female (8.2 ± 2.5). In regard to sex ratio affecting progeny production, oviposition was greatest with only one male. Mixed results were obtained in light verses dark conditions and further experiments regarding the effects of day length on oviposition would be useful for optimizing oviposition of D. maculatus.     

New perspectives on perfluorochemical ecotoxicology: inhibition and induction of an efflux transporter in the marine mussel, Mytilus californianus

The toxicological effects of perfluoroalkyl acids on the p-glycoprotein (p-gp) cellular efflux transporter were investigated using the marine mussel Mytilus californianus as a model system. Four of the perfluoroalkyl acids studied exhibit chemosensitizing behavior, significantly inhibiting p-gp transporter activity. The inhibitory potency is maximal for the longer chain acids perfluorononanoate (PFNA) and perfluorodecanoate (PFDA), with average IC50 values of 4.8 and 7.1 microM, respectively. Results indicate that PFNA inhibits p-gp by an indirect mechanism, and this inhibition is reversible and accompanied by a rapid loss of PFNA from the tissue. In addition, PFNA induces expression of the p-gp transporter after a 2-h exposure, a stress response that may result in a metabolic cost to the organism. Given that most organisms, including humans, share efflux transporters as a first line of defense against toxicants, the results of this study may have broader implications for the ecotoxicology of perfluoroalkyl acids.     

Solving problems resulting from solutions: evolution of a dual nutrient management strategy for the eutrophying Neuse River Estuary, North Carolina

In estuaries, phosphorus (P) and nitrogen (N) inputs generally control freshwater and saltwater primary production, respectively. Improved wastewater P removal and a P-detergent ban in the late 1980s decreased P loading to the nutrient over-enriched Neuse River Estuary, NC, without a contemporaneous reduction in N loading. This led to a decrease in upstream freshwater phytoplankton production and a reduction in nuisance algal blooms. While this nutrient management approach appeared to be effective in reducing the symptoms of freshwater eutrophication, it may have also diminished the upstream algal N filter, promoting N enrichment, relative to P enrichment, and eutrophication of the more saline downstream N-limited waters. Recent N controls implemented by the State of North Carolina should help address the problem. These findings underscore the need for watershed- and basin-scale, dual nutrient (N and P) reduction strategies that consider the entire freshwater--marine continuum as well as hydrologic variability (e.g., hurricanes, floods, droughts) when formulating long-term controls of estuarine eutrophication.     

Levels and enantiomeric signatures of methyl sulfonyl PCB and DDE metabolites in livers of harbor porpoises (Phocoena phocoena) from the Southern North Sea

The concentration of 26 methyl sulfonyl metabolites of polychlorinated biphenyls (MeSO2-PCBs) and of p,p'-DDE (MeSO2-DDE) were determined in 19 liver samples from harbor porpoises (Phocoena phocoena) stranded between 1997 and 2000 on the Belgian and French North Sea Coasts. The total concentration of MeSO2-PCBs ranged from 39 to 4221 ng/g lipid weight (lw) and were generally higher in adults (age > 2 yr, range 969-4,221 ng/g lw) than in juveniles (age < 2 yr, range 39-1815 ng/g lw). The concentrations of MeSO2-DDE were generally also higher in adults (21-96 ng/g lw) than in juveniles (0.5-60 ng/g lw). Congeners 3- and 4-MeSO2-CB101 were the dominating metabolites in all samples. Due to their preferential retention in the liver, the MeSO2-PCB congeners could be divided into two groups. The first group was dominated by the 3-MeSO2-PCB congeners and consisted of MeSO2-CB31, -CB49, -CB52, -CB87, and -CB101, which all have a 2,5-chlorine substitution in the phenyl ring containing the methyl sulfonyl group. The second group was dominated by the 4-MeSO2-PCB congeners and consisted of MeSO2-CB64, -CB91, -CB110, and -CB132, which all have a 2,3,6-chlorine substitution. The ratios of sum of PCBs/sum of MeSO2-PCBs and p,p'-DDE/MeSO2-DDE differed greatly between individual subjects and ranged from 15 to 419 and from 17 to 1088, respectively. The ratio between the precursor PCB congeners and their corresponding metabolites ranged from 0.6 (CB49) to 175 (CB174). Enantiomeric fractions (EFs) for MeSO2-PCB atropisomers, which include 3-MeSO2-CB132, 3-MeSO2-CB149, 4-MeSO2-CB149, 3-MeSO2-CB174, and 4-MeSO2-CB174, were also measured in 8 out of the 19 subjects. High enantiomeric excess (EF > 0.73 or EF < 0.23) for the measured chiral MeSO2-PCB congeners was found in all samples. This result may suggest that one atropisomer may be preferentially formed in harbor porpoises or that the atropisomers are retained in a highly selective manner.     

Cadmium bioavailability and accumulation in the presence of humic acid to the zebra mussel, Dreissena polymorpha

Metal speciation in aquatic systems is mainly determined by the type and concentration of ligands present in solution. A very important group of complexing agents is dissolved organic matter (DOM), e.g., humic and fulvic acids. According to the free-ion activity model, only the free metal ion is available to biota. Nevertheless, DOM has been reported to decrease or increase metal uptake, leading to uncertainty concerning the bioavailability of metal-DOM complexes. In this work the effect of Aldrich humic acid on cadmium accumulation by the zebra mussel, Dreissena polymorpha, was studied under laboratory conditions. Mussels, collected in a drinking water reservoir, were exposed to varying environmentally relevant concentrations of cadmium in the presence and absence of humic acid. Cadmium concentrations in the mussel tissues were analyzed, and measurements with a cadmium-ion-selective electrode were made to determine the free cadmium ion activity in the exposure waters. The uptake of humic acid by the zebra mussels was measured by the decrease of the total organic carbon (TOC) concentration in the water over time. The free cadmium ion activity in the water decreased from 51.6% to 19.9% of the total cadmium concentration in the presence of humic acid. This decrease by a factor of 2.6 resulted in a decrease in the cadmium uptake rate in the soft tissue of zebra mussels from 12.9 to 7.9 nmol/g dry wt/day, which corresponds to a decrease by a factor of 1.6. This implies that cadmium uptake rates were higher than predicted by the free-ion activity model and indicates that cadmium-humic acid complexes are partly available to zebra mussels.     

Beryllium-7 as a tracer of short-term sediment deposition and resuspension in the Fox River, Wisconsin

Short-term (approximately monthly) sediment deposition and resuspension rates of surficial bed sediments in two PCB-laden impoundments on the Fox River, WI, were determined in the summer and fall of 1998 using 7Be, a naturally occurring radioisotope produced in the atmosphere. Decay-corrected activities and inventories of 7Be were measured in bed sediment and in suspended particles. Beryllium-7 activities generally decreased with depth in the top 5-10 cm of sediments and ranged from undetectable to approximately 0.9 pCi cm(-3). Inventories of 7Be, calculated from the sum of activities from all depths, ranged from 0.87 to 3.74 pCi cm(-2), and the values covaried between sites likely reflecting a common atmospheric input signal. Activities of 7Be did not correlate directly with rainfall. Partitioning the 7Be flux into "new" and "residual" components indicated that net deposition was occurring most of the time during the summer. Net erosion, however, was observed at the upstream site from the final collection in the fall. This erosion event was estimated to have removed 0.10 g (cm of sediment)(-2), corresponding to approximately 0.5 cm of sediment depth, and approximately 6-10 kg of polychlorinated biphenyls (PCBs) over the whole deposit. Short-term accumulation rates were up to approximately 130 times higher than the long-term rates calculated from 137Cs profiles, suggesting an extremely dynamic sediment transport environment, even within an impounded river system.     

Evaluating bacteriophage P22 as a tracer in a complex surface water system: the Grand River, Michigan

Viruses are important pathogens in both marine and fresh water environments. There is a strong interest in using bacteriophages as tracers because of their role as model viruses, since dissolved chemical tracers may not adequately describe the behavior of viruses that are suspended colloids. Despite a large number of studies that examined the transport of bacteriophages in the subsurface environment, few studies examined phage transport in large and complex surface water systems. In this paper we report the results of a dual tracer study on a 40 km reach of the Grand River, the longest river in Michigan, and we examine the performance of bacteriophage P22 relative to a chemical tracer (Rhodamine WT). Our analysis based on the transient storage (TS) model indicated that P22 can be successfully used as a tracer in complex surface water environments. Estimated P22 inactivation rates were found to be in the range 0.27-0.57 per day (0.12-0.25 log10 per day). The highest inactivation rate was found in a reach with high suspended solids concentration, relatively low dissolved organic carbon content, and sediment with high clay content. Estimated TS model parameters for both tracers were found to be consistent with surficial geology and land use patterns. Maximum storage zone sizes for the two tracers were found in different river reaches, indicating that different processes contributed to TS within the same reach for the two tracers. This model can be used to examine the arrival times and concentrations of human viral pathogens released from untreated sewage at recreational areas.     

Effects of seabird vectors on the fate, partitioning, and signatures of contaminants in a High Arctic ecosystem

Seabirds bioaccumulate contaminants from prey, transport them to their nesting sites, and deposit them in their excreta and carcasses, thereby focusing marine-derived contaminants into remote, terrestrial receptor sites. In the case of organochlorine chemicals transported by northern fulmars (Fulmarus glacialis) to a High Arctic seabird colony on Devon Island, Nunavut, Canada (76°13'N, 89°14'W), this contaminant pathway dominates all others. In freshwater ponds below the nesting cliffs, concentrations of organochlorine contaminants characteristic of fulmar input were 2- to 45-fold higher in sediments and water (depending on seabird input to the particular pond) than in ponds remote from the colony. Air-water fugacity quotients for the ponds decreased with seabird input, indicating that fulmar contaminant input shifts air-water partitioning to increasingly favor volatilization to air. Although contaminant evasion from water was favored, direct evidence of it was not detected in air samples. For PCBs, congener profiles of pond sediments or water became more similar to seabird sources as seabird input increased, and less similar to air profiles. Based on measurements of contaminants in fulmars and other local environmental media, this study presents the first application of fugacities and multivariate source apportionment statistics to resolve seabird biological vectors.     

全球粮食系统可持续性与安全:石油峰值、气候变化及淡水缺乏所带来的挑战

在2007-2008年间,由于农产品价格的大幅上升以及全球粮食储备量的锐减,使人们对粮食安全更加关注.     

PCDDs, PCDFs, and coplanar PCBs in albatross from the North Pacific and Southern Oceans: levels, patterns, and toxicological implications

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (coplanar PCBs) were determined in five albatross species collected from the North Pacific and Southern Oceans to assess the north-south differences in residue levels, accumulation patterns, and toxic potential. Black-footed and Laysan albatrosses from the North Pacific Ocean contained higher levels of PCDD/Fs and coplanar PCBs than albatrosses from the Southern Ocean, indicating that emission sources of these contaminants were predominant in the northern hemisphere. Residue levels in albatrosses from the remote North Pacific Ocean far from the point source of pollution were comparable to or higher than those in terrestrial and coastal birds from contaminated areas in developed nations, suggesting the specific exposure and accumulation of PCDD/Fs and coplanar PCBs in albatross. The long life span and ingestion of plastic resin pellets by albatrosses could be the plausible explanations for the elevated accumulation of persistent and lipophilic contaminants including PCDD/Fs and coplanar PCBs in these birds. Relative proportions of PCDFs and coplanar PCBs in albatross were higher than those observed in birds inhabiting terrestrial and coastal areas, suggesting that these toxic chemicals may have higher transportability by air and water than PCDDs. Congener patterns of PCDD/Fs in albatross showed less variability as compared to those in terrestrial species, indicating that contamination patterns of PCDD/Fs were similar within the open ocean environment. Contributions of PCDD/Fs to total TEQs in albatrosses from the open ocean were generally lower than those in terrestrial birds, suggesting different toxic potency of PCDD/Fs and coplanar PCBs on animals inhabiting open ocean and terrestrial environment. Whereas albatrosses from southern oceans retained lower TEQ concentrations, possible adverse effects of PCDD/Fs and coplanar PCBs to black-footed and Laysan albatrosses of the North Pacific Ocean may be suspected from TEQ levels.