Source apportionment of circum-Arctic atmospheric black carbon from isotopes and modeling.

Black carbon (BC) contributes to Arctic climate warming, yet source attributions are inaccurate due to lacking observational constraints and uncertainties in emission inventories. Year-round, isotope-constrained observations reveal strong seasonal variations in BC sources with a consistent and synchronous pattern at all Arctic sites. These sources were dominated by emissions from fossil fuel combustion in the winter and by biomass burning in the summer. The annual mean source of BC to the circum-Arctic was 39 ± 10% from biomass burning. Comparison of transport-model predictions with the observations showed good agreement for BC concentrations, with larger discrepancies for (fossil/biomass burning) sources. The accuracy of simulated BC concentration, but not of origin, points to misallocations of emissions in the emission inventories. The consistency in seasonal source contributions of BC throughout the Arctic provides strong justification for targeted emission reductions to limit the impact of BC on climate warming in the Arctic and beyond.

Rare and Common Variants Conferring Risk of Tooth Agenesis.

We present association results from a large genome-wide association study of tooth agenesis (TA) as well as selective TA, including 1,944 subjects with congenitally missing teeth, excluding third molars, and 338,554 controls, all of European ancestry. We also tested the association of previously identified risk variants, for timing of tooth eruption and orofacial clefts, with TA. We report associations between TA and 9 novel risk variants. Five of these variants associate with selective TA, including a variant conferring risk of orofacial clefts. These results contribute to a deeper understanding of the genetic architecture of tooth development and disease. The few variants previously associated with TA were uncovered through candidate gene studies guided by mouse knockouts. Knowing the etiology and clinical features of TA is important for planning oral rehabilitation that often involves an interdisciplinary approach.

15q11.2 CNV affects cognitive, structural and functional correlates of dyslexia and dyscalculia.

Several copy number variants have been associated with neuropsychiatric disorders and these variants have been shown to also influence cognitive abilities in carriers unaffected by psychiatric disorders. Previously, we associated the 15q11.2(BP1-BP2) deletion with specific learning disabilities and a larger corpus callosum. Here we investigate, in a much larger sample, the effect of the 15q11.2(BP1-BP2) deletion on cognitive, structural and functional correlates of dyslexia and dyscalculia. We report that the deletion confers greatest risk of the combined phenotype of dyslexia and dyscalculia. We also show that the deletion associates with a smaller left fusiform gyrus. Moreover, tailored functional magnetic resonance imaging experiments using phonological lexical decision and multiplication verification tasks demonstrate altered activation in the left fusiform and the left angular gyri in carriers. Thus, by using convergent evidence from neuropsychological testing, and structural and functional neuroimaging, we show that the 15q11.2(BP1-BP2) deletion affects cognitive, structural and functional correlates of both dyslexia and dyscalculia.

Metabolite mapping by consecutive nanostructure and silver-assisted mass spectrometry imaging on tissue sections.

RATIONALE: Nanostructure-based mass spectrometry imaging (MSI) is a promising technology for molecular imaging of small molecules, without the complex chemical background typically encountered in matrix-assisted molecular imaging approaches. Here, we have enhanced these surfaces with silver (Ag) to provide a second tier of MSI data from a single sample. METHODS: MSI data was acquired through the application of laser desorption/ionization mass spectrometry to biological samples imprinted onto desorption/ionization on silicon (DIOS) substrates. Following initial analysis, ultra-thin Ag layers were overlaid onto the followed by MSI analysis (Ag-DIOS MSI). This approach was first demonstrated for fingermark small molecules including environmental contaminants and sebum components. Subsequently, this bimodal method was translated to lipids and metabolites in fore-stomach sections from a 6-bromoisatin chemopreventative murine mouse model. RESULTS: DIOS MSI allowed mapping of common ions in fingermarks as well as 6-bromoisatin metabolites and lipids in murine fore-stomach. Furthermore, DIOS MSI was complemented by the Ag-DIOS MSI of Ag-adductable lipids such as wax esters in fingermarks and cholesterol in murine fore-stomach. Gastrointestinal acid condensation products of 6-bromoisatin, such as the 6,6'-dibromoindirubin mapped herein, are very challenging to isolate and characterize. By re-analyzing the same tissue imprints, this metabolite was readily detected by DIOS, placed in a tissue-specific spatial context, and subsequently overlaid with additional lipid distributions acquired using Ag-DIOS MSI. CONCLUSIONS: The ability to place metabolite and lipid classes in a tissue-specific context makes this novel method suited to MSI analyses where the collection of additional information from the same sample maximises resource use, and also maximises the number of annotated small molecules, in particular for metabolites that are typically undetectable with traditional platforms. Copyright © 2017 John Wiley & Sons, Ltd.

Massive remobilization of permafrost carbon during post-glacial warming.

Recent hypotheses, based on atmospheric records and models, suggest that permafrost carbon (PF-C) accumulated during the last glaciation may have been an important source for the atmospheric CO2 rise during post-glacial warming. However, direct physical indications for such PF-C release have so far been absent. Here we use the Laptev Sea (Arctic Ocean) as an archive to investigate PF-C destabilization during the last glacial-interglacial period. Our results show evidence for massive supply of PF-C from Siberian soils as a result of severe active layer deepening in response to the warming. Thawing of PF-C must also have brought about an enhanced organic matter respiration and, thus, these findings suggest that PF-C may indeed have been an important source of CO2 across the extensive permafrost domain. The results challenge current paradigms on the post-glacial CO2 rise and, at the same time, serve as a harbinger for possible consequences of the present-day warming of PF-C soils.

The sources of atmospheric black carbon at a European gateway to the Arctic.

Black carbon (BC) aerosols from incomplete combustion of biomass and fossil fuel contribute to Arctic climate warming. Models-seeking to advise mitigation policy-are challenged in reproducing observations of seasonally varying BC concentrations in the Arctic air. Here we compare year-round observations of BC and its δ(13)C/Δ(14)C-diagnosed sources in Arctic Scandinavia, with tailored simulations from an atmospheric transport model. The model predictions for this European gateway to the Arctic are greatly improved when the emission inventory of anthropogenic sources is amended by satellite-derived estimates of BC emissions from fires. Both BC concentrations (R(2)=0.89, P<0.05) and source contributions (R(2)=0.77, P<0.05) are accurately mimicked and linked to predominantly European emissions. This improved model skill allows for more accurate assessment of sources and effects of BC in the Arctic, and a more credible scientific underpinning of policy efforts aimed at efficiently reducing BC emissions reaching the European Arctic.

Activation of old carbon by erosion of coastal and subsea permafrost in Arctic Siberia.

The future trajectory of greenhouse gas concentrations depends on interactions between climate and the biogeosphere. Thawing of Arctic permafrost could release significant amounts of carbon into the atmosphere in this century. Ancient Ice Complex deposits outcropping along the ~7,000-kilometre-long coastline of the East Siberian Arctic Shelf (ESAS), and associated shallow subsea permafrost, are two large pools of permafrost carbon, yet their vulnerabilities towards thawing and decomposition are largely unknown. Recent Arctic warming is stronger than has been predicted by several degrees, and is particularly pronounced over the coastal ESAS region. There is thus a pressing need to improve our understanding of the links between permafrost carbon and climate in this relatively inaccessible region. Here we show that extensive release of carbon from these Ice Complex deposits dominates (57 ± 2 per cent) the sedimentary carbon budget of the ESAS, the world's largest continental shelf, overwhelming the marine and topsoil terrestrial components. Inverse modelling of the dual-carbon isotope composition of organic carbon accumulating in ESAS surface sediments, using Monte Carlo simulations to account for uncertainties, suggests that 44 ± 10 teragrams of old carbon is activated annually from Ice Complex permafrost, an order of magnitude more than has been suggested by previous studies. We estimate that about two-thirds (66 ± 16 per cent) of this old carbon escapes to the atmosphere as carbon dioxide, with the remainder being re-buried in shelf sediments. Thermal collapse and erosion of these carbon-rich Pleistocene coastline and seafloor deposits may accelerate with Arctic amplification of climate warming.

Copy number variations of chromosome 16p13.1 region associated with schizophrenia.

Deletions and reciprocal duplications of the chromosome 16p13.1 region have recently been reported in several cases of autism and mental retardation (MR). As genomic copy number variants found in these two disorders may also associate with schizophrenia, we examined 4345 schizophrenia patients and 35,079 controls from 8 European populations for duplications and deletions at the 16p13.1 locus, using microarray data. We found a threefold excess of duplications and deletions in schizophrenia cases compared with controls, with duplications present in 0.30% of cases versus 0.09% of controls (P=0.007) and deletions in 0.12 % of cases and 0.04% of controls (P>0.05). The region can be divided into three intervals defined by flanking low copy repeats. Duplications spanning intervals I and II showed the most significant (P = 0.00010) association with schizophrenia. The age of onset in duplication and deletion carriers among cases ranged from 12 to 35 years, and the majority were males with a family history of psychiatric disorders. In a single Icelandic family, a duplication spanning intervals I and II was present in two cases of schizophrenia, and individual cases of alcoholism, attention deficit hyperactivity disorder and dyslexia. Candidate genes in the region include NTAN1 and NDE1. We conclude that duplications and perhaps also deletions of chromosome 16p13.1, previously reported to be associated with autism and MR, also confer risk of schizophrenia.

Expanding the range of ZNF804A variants conferring risk of psychosis.

A trio of genome-wide association studies recently reported sequence variants at three loci to be significantly associated with schizophrenia. No sequence polymorphism had been unequivocally (P<5 × 10(-8)) associated with schizophrenia earlier. However, one variant, rs1344706[T], had come very close. This polymorphism, located in an intron of ZNF804A, was reported to associate with schizophrenia with a P-value of 1.6 × 10(-7), and with psychosis (schizophrenia plus bipolar disorder) with a P-value of 1.0 × 10(-8). In this study, using 5164 schizophrenia cases and 20,709 controls, we replicated the association with schizophrenia (odds ratio OR = 1.08, P = 0.0029) and, by adding bipolar disorder patients, we also confirmed the association with psychosis (added N = 609, OR = 1.09, P = 0.00065). Furthermore, as it has been proposed that variants such as rs1344706[T]-common and with low relative risk-may also serve to identify regions harboring less common, higher-risk susceptibility alleles, we searched ZNF804A for large copy number variants (CNVs) in 4235 psychosis patients, 1173 patients with other psychiatric disorders and 39,481 controls. We identified two CNVs including at least part of ZNF804A in psychosis patients and no ZNF804A CNVs in controls (P = 0.013 for association with psychosis). In addition, we found a ZNF804A CNV in an anxiety patient (P = 0.0016 for association with the larger set of psychiatric disorders).

Soluble urokinase plasminogen activator receptor as a prognostic marker in men participating in prostate cancer screening.

BACKGROUND: The urokinase plasminogen activator (uPA) system is involved in tissue remodelling processes and is up-regulated in many types of malignancies. We investigated whether serum levels of different forms of soluble uPA receptor (suPAR) are associated with survival and in particular with prostate cancer and cardiovascular disease mortality. METHODS: Using time-resolved fluorescence immunoassays, we measured intact suPAR [suPAR(I-III)] and intact plus cleaved suPAR [suPAR(I-III) + suPAR(II-III)] and thus calculated the amount of suPAR(II-III) in serum samples from 375 men participating in a prostate cancer screening trial. A total of 312 men were free of prostate cancer and 63 men had prostate cancer diagnosed at the time of screening. The cohort was followed for 15 years. We assessed survival using Kaplan-Meier estimation and Cox proportional hazards regression. RESULTS: The mean age at blood sampling was 64 years. In total, 152 men died during follow-up. SuPAR(I-III) and suPAR(II-III) were significantly positively associated with mortality (P = 0.001 and P < 0.0001, respectively). In a Cox regression model adjusting for age and prostate cancer status, an increase in suPAR(I-III) and suPAR(II-III) by 1-unit (ln-scale) was associated with a hazard ratio (HR) of 2.26 [95% confidence interval (CI) 1.17-4.35] and 2.53 (95% CI 1.56-4.10), respectively. There was a trend towards an increased risk of death from prostate cancer in screening-detected prostate cancer patients with increased values of either suPAR form. However, this difference was not significant and the association disappeared after adjusting for age, tumour stage, tumour grade and prostate-specific antigen. Being in the highest quartile of any of the suPAR forms was associated with a highly significant increased risk of cardiovascular death, with HR adjusted for age of 3.27 (95% CI 1.38-7.73) for suPAR(I-III) quartile 4 versus quartile 1. Conclusions. High concentrations of serum suPAR(I-III) and suPAR(II-III) were associated with poor overall survival. The association was particularly strong for death from cardiovascular disease. No similar association was found for prostate cancer after adjustment for other prognostic factors.

Early evolution of multifocal optics for well-focused colour vision in vertebrates.

Jawless fishes (Agnatha; lampreys and hagfishes) most closely resemble the earliest stage in vertebrate evolution and lamprey-like animals already existed in the Lower Cambrian [about 540 million years ago (MYA)]. Agnathans are thought to have separated from the main vertebrate lineage at least 500 MYA. Hagfishes have primitive eyes, but the eyes of adult lampreys are well-developed. The southern hemisphere lamprey, Geotria australis, possesses five types of opsin genes, three of which are clearly orthologous to the opsin genes of jawed vertebrates. This suggests that the last common ancestor of all vertebrate lineages possessed a complex colour vision system. In the eyes of many bony fishes and tetrapods, well-focused colour images are created by multifocal crystalline lenses that compensate for longitudinal chromatic aberration. To trace the evolutionary origins of multifocal lenses, we studied the optical properties of the lenses in four species of lamprey (Geotria australis, Mordacia praecox, Lampetra fluviatilis and Petromyzon marinus), with representatives from all three of the extant lamprey families. Multifocal lenses are present in all lampreys studied. This suggests that the ability to create well-focused colour images with multifocal optical systems also evolved very early.

Leaching of metals from sewage sludge during one year and their relationship to particle size.

Leaching of metals from sewage sludge can lead to their accumulation in topsoil and can also contaminate groundwater. Our objectives were to document the metal leachates and the size distribution of leached particles from sewage sludge and to identify possible correlations with physical factors. Results from monthly lysimeter sampling showed an initial release followed by decline for most metals. Cadmium, Ca, Sr, Li, Mn, Ni and Zn showed a "cyclic" behaviour. Filtration revealed that this "cyclicity" had no correlation to the size of released particles, but Al, Cr, Fe, Cu, Ag and Pb were clearly related to release of coarser particles most of the year. Total metal amounts leached during one year, relative to original sludge content, had the order Na>Ca=Mg>Mn>Sr>Zn>K>Li=Ni>Cd>Co>Rb>Ag>Cr>Ba=Cu>Ga>Al=Pb=Fe. There were no simple correlations between monthly measured leachate concentrations and precipitation, temperature or pH of precipitation. Occasional leachate sampling might give misleading values for metals with "cyclic" behaviour.

Observations of the PCB distribution within and in-between ice, snow, ice-rafted debris, ice-interstitial water, and seawater in the Barents Sea marginal ice zone and the North Pole area.

To evaluate the two hypotheses of locally elevated exposure of persistent organic pollutants (POPs) in ice-associated microenvironments and ice as a key carrier for long-range transport of POPs to the Arctic marginal ice zone (MIZ), dissolved and particulate polychlorinated biphenyls (PCBs) were analyzed in ice, snow, ice-interstitial water (IIW), seawater in the melt layer underlying the ice, and in ice-rafted sediment (IRS) from the Barents Sea MIZ to the high Arctic in the summer of 2001. Ultra-clean sampling equipment and protocols were specially developed for this expedition, including construction of a permanent clean room facility and a stainless steel seawater intake system on the I/B ODEN as well as two mobile 370 l ice-melting systems. Similar concentrations were found in several ice-associated compartments. For instance, the concentration of one of the most abundant congeners, PCB 52, was typically on the order of 0.1-0.3 pg l(-1) in the dissolved (melted) phase of the ice, snow, IIW, and underlying seawater while its particulate organic-carbon (POC) normalized concentrations were around 1-3 ng gPOC(-1) in the ice, snow, IIW, and IRS. The solid-water distribution of PCBs in ice was well correlated with and predictable from K(ow) (ice log K(oc)-log K(ow) regressions: p<0.05, r2=0.78-0.98, n=9), indicating near-equilibrium partitioning of PCBs within each local ice system. These results do generally not evidence the existence of physical microenvironments with locally elevated POP exposures. However, there were some indications that the ice-associated system had harbored local environments with higher exposure levels earlier/before the melting/vegetative season, as a few samples had PCB concentrations elevated by factors of 5-10 relative to the typical values, and the elevated levels were predominantly found at the station where melting had putatively progressed the least. The very low PCB concentrations and absence of any significant concentration gradients, both in-between different matrices and over the Eurasian Arctic basin scale, suggest that ice is not an important long-range transport purveyor of POPs to the Arctic MIZ ecosystem.

MR follow-up of small experimental intracranial haemorrhages from hyperacute to subacute phase.

PURPOSE: To compare pulse sequences in revealing intracranial bleeding from the hyperacute to subacute phase. MATERIAL AND METHODS: We injected 0.3-1 ml of autologous blood into the brain of 8 rabbits. MR imaging was performed immediately after haematoma creation and then at determined intervals up to 9-12 days. All images were analysed by two observers. After the last MR investigation, the brain was fixed in formalin. The last MR images were compared to the fixed brain sections and to the histologic findings. RESULTS: T2*-weighted GE sequences, both conventional spoiled and echoplanar sequences, revealed the intraparenchymal haematomas as hypointensities in all but 1 case, which was negative from the second day onward (a rabbit with 0.3 ml blood injected). The signal patterns remained unchanged during the follow-up. The haematoma sizes and shapes corresponded well to gross pathology. Blood in the cerebrospinal fluid (CSF) space was detected with T2*-weighted GE sequences in a great majority of the examinations during the first 2 days. The cases with the smallest injected volume of blood were negative. SE sequences were rather insensitive. The FLAIR sequence often revealed blood in CSF spaces but not in the brain. CONCLUSION: T2*-weighted GE sequences are capable of revealing very small intraparenchymal haemorrhages from the hyperacute to the subacute phase, and blood in CSF spaces during at least the first 2 days.

A Critical Evaluation of Interlaboratory Data on Total, Elemental, and Isotopic Carbon in the Carbonaceous Particle Reference Material, NIST SRM 1649a.

Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST "urban dust" Standard Reference Material(®) SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of ((14)C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction). A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) (14)C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and (14)C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of isotopic mass balance.

Soot-carbon influenced distribution of PCDD/Fs in the marine environment of the Grenlandsfjords, Norway.

The particle associations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were studied in both the water column and the surface sediments of a marine fiord system and were found to poorly obey expectations from the organic matter partitioning (OMP) paradigm. The field observations were instead consistent with the presence of a stronger sorbent subdomain such as pyrogenic soot-carbon (SC) playing an important role in affecting the environmental distribution and fate of PCDD/Fs. Solid-water distribution coefficients (Kd) of PCDD/ Fs actually observed in the water column were several orders of magnitude above predictions from a commonly used OMP model. Even when these elevated Kd values were normalized to the particulate organic carbon (POC) content (i.e., K(OC)), the variability in K(OC) for individual PCDD/ Fs at different fjord locations and seasons of factors 100-1,000 suggested that bulk organic matter was not the governing sorbent domain of the suspended particles. Further, POC-normalized particle concentrations of PCDD/ Fs (C(OC)) in a vertical profile (surface water-bottom water-surface sediment) revealed a strong increasing trend with depth. Factors of about 100 higher Coc for all PCDD/Fs in the sediment than in the surface water could not be explained by higher fugacity in the surrounding deep water nor with C:N or delta13C indexes of selective aging of the bulk organic matter. Instead this was hypothesized to reflect selective preservation of a more recalcitrant and highly sorbing, but minor, subdomain such as soot. The extent of enhanced PCDD/F sorption, above the OMP predictions, was positively correlated with the SC:POC ratio of the suspended particles in surface and deep waters. Finally, the geographical distribution of sedimentary PCDD/F concentrations were better explained by the SC content than by the bulk OC content of the sediment. Altogether, these field-based findings add to recent laboratory-based sorption studies to suggest that we need to consider both amorphous OC partitioning domains and SC particles as carriers of planar aromatic contaminants if we are to explain the environmental distribution and fate of pollutants such as PCDD/Fs.

Process-diagnostic patterns of chlorobiphenyl congeners in two radiochronologically characterized sediment cores from the northern Baffin Bay.

Polychlorinated biphenyl (PCB) patterns were interpreted in two radioisotopically constrained sediment cores from the Arctic ocean in order to seek clues about their large-scale environmental fates. Low but clearly measurable fluxes of individual PCB congeners were observed in deeper layer sediments, corresponding to the past 170 years, in a single dated core from the Baffin Bay shelf. Fluxes of the dominant individual congeners in the surface sediments were 20-100 pg m(-2) d(-1). Combining these data with the sediment data from the Arctic Monitoring and Assessment Program, it appears that the PCB distribution in Arctic surface sediments is governed by the organic carbon (OC) content of the sediments. The historical development of the PCB congener fingerprint suggests that the modern sediments are enriched in medium-chlorinated congeners, implying that there are at least two significant, but distinctly different, sink processes acting on the PCB pool. The relative abundance of light-to-heavy congeners, in mid-shelf marine sediments of similar ages, between 40 degrees N and 76 degrees N latitude suggests a northward dilution of PCBs which is stronger attenuated for heavier congeners, consistent with a temperature-driven global fractionation process. The significant presence of PCB in historical archives pre-dating the organochlorine society, as observed in this and several previous studies, awaits a fuller explanation.

Dynamic colloid--water partitioning of pyrene through a coastal Baltic spring bloom.

Colloidal organic particles constitute the dominant portion of particulate organic matter in surface seawater, but their influence on the phase speciation and bioavailability of hydrophobic organic compounds (HOCs) is sparsely evaluated. Studies on colloid-water partitioning have been focused on other regimes and have largely been performed on chemically defined subportions of total colloids such as the humic fraction. Available estimates of colloid-water partition coefficients (Kcoc) are highly variable and not easily explained by regularly applied Kow-Koc relationships. Here, pyrene was partitioned to bulk natural colloids isolated using cross-flow ultrafiltration techniques from the surface water of a coastal bay. A key objective was to elucidate biogeochemical controls on the changing colloid-sorbent qualities over the course of the dynamic allochtonous-autochtonous transition of a well-constrained boreal coastal spring bloom. The pyrene Kcoc was found to decrease from 12.9+/-0.9 x 10(3) Lw/kg(oc) in the terrestrial runoff dominated regime to values around 2.9+/-0.7 x 10(3) Lw/kg(oc), once phytoplankton production became the governing source of organic matter to the surface waters. The changing Kcoc was well correlated with the molar extinction coefficient at 280 nm of the colloidal organic carbon. This study supports other reports of an improved prediction of HOC phase speciation through this simple molecular proxy of the "quality" of organic sorbents. While being poor sorbents on a carbon atom basis, relative to soils and sediments, coastal marine colloids, by their shear abundance, may significantly attenuate the truly dissolved exposures of HOCs with log Kow above 5.

Ubiquitous observations of enhanced solid affinities for aromatic organochlorines in field situations: are in situ dissolved exposures overestimated by existing partitioning models?

This paper investigates the ability of the traditional organic matter partitioning (OMP) model to predict the solid-water distribution, and hence the dissolved exposures, of hydrophobic organic compounds (HOCs) in real field situations. Observed organic-carbon-normalized partitioning coefficients (Koc)obs) of polychlorinated biphenyls, polychlorinated benzenes, polychlorinated dibenzo-dioxins and -furans, and p,p'-dichlorodiphenyltrichlorethane (DDT) with metabolites were selected from the literature and compared with their respective OMP model estimates. For all compound classes and in a majority of the investigated cases, (Koc)obs values were significantly larger than predicted. This translated into factors of overestimated dissolved exposures ranging from 1 to 1,000. Various reasons are discussed for the discrepancies between predictions and actual observations, such as the effect of the diagenetic state and other properties of the particulate organic matter. The greater enhancement in (Koc)obs of planar over nonplanar compounds suggests in certain cases that efficient interactions with aromatic soot phases may be significant. For an improved predictability of (Koc)obs and dissolved exposures of HOCs in the real environment, the inclusion of soot and possibly other distinct subfractions of bulk organic carbon into an extended solid-water partitioning model may be considered.

Fate of linear alkylbenzenes released to the coastal environment near Boston Harbor.

Linear alkylbenzenes (LABs) were used to assess the fates of hydrophobic organic compounds (HOCs) released to a large urban harbor and the adjoining offshore waters. We found that particulate concentrations of the individual C12 LAB isomers in 1996 summertime surface waters decreased from 1 pM in Boston Harbor to 20-200 fM in coastal Massachusetts and Cape Cod Bays. Levels fell to only a few fM in offshore Gulf of Maine locations. These observations were consistent with municipal wastewater in Boston Harbor as the predominant input followed by dispersal via known circulation patterns in this region. Phase-dependent removal rate coefficients for flushing, vertical scavenging, volatilization, photodegradation, and biodegradation of individual LAB isomers were constrained from literature, field observations, and laboratory experiments and combined with estimates of wastewater release rates into a predictive 3-box model. Vertical scavenging, biodegradation, and flushing were predicted to be the most important fate processes for C12 LABs in the Boston Harbor-MA Bay-Cape Cod Bay flow system with about 1% of the harbor releases "surviving" passage. For HOCs such as the relatively bio-recalcitrant LAB, 6-phenyldodecane, it appears that we are at present able to predict the coastal fate of harbor-introduced HOCs in this system within a factor of 2. Contrary to expectations from biodegradation experiments, the ratio of internal-to-external (I/E) LAB isomers decreased offshore in both water and sediment samples, suggesting we are "missing" an important process affecting LAB fates.