Degradation of picric acid and 2,6-DNT in marine sediments and waters: the role of microbial activity and ultra-violet exposure

Bio- and photo-transformation of two munitions and explosives of concern, 2,6-dinitrotoluene (2,6-DNT) and 2,4,6-trinitrophenol (picric acid) were assessed in spiked marine sediments and water. A sandy and a fine-grained sediment, with 0.25% and 1.1% total organic carbon, respectively, were used for biotransformation assessments at 10 and 20 degrees C. Sterilized sediments were used as controls for biotic vs. abiotic transformation. Transformation products were analyzed by HPLC, GC/MS and LC/MS. Biotransformation in sediments started soon after the initial contact of the chemicals with the sediments and proceeded for several months, with rates in the following sequence: fine-grain at 20 degrees C > fine-grain at 10 degrees C > sand at 20 degrees C > sand at 10 degrees C. The biotransformation paths seemed to be similar for all conditions. The major biotransformation product of 2,6-DNT was 2-amino-6-nitrotoluene (2-A-6-NT). 2-Nitrotoluene (2-NT) and other minor components, including N,N-dimethyl-3-nitroaniline, benzene nitrile, methylamino-2-nitrosophenol and diaminophenol, were also identified. After more prolonged incubation these chemicals were replaced by high molecular weight polymers. Several breakdown products of picric acid were identified by GC/MS, including 2,4-dinitrophenol, amino dinitrophenols, 3,4-diamino phenol, amino nitrophenol and nitro diaminophenol. Photo-transformation of 2,6-DNT and picric acid in seawater was assessed under simulated solar radiation (SSR). No significant photolysis of picric acid in seawater was observed for up to 47 days, but photo-transformation of 2,6-DNT began soon after the initial exposure to SSR, with 89% being photo-transformed in 24 h and none remaining after 72 h. High molecular weight chemicals were generated, with mass spectra ranging from molecular weight 200-500 compared to 182 for DNT, and the color of the stock solution changed from clear to orange. Complexity of the mass spectra and mass differences among fragments suggest that multiple polymers were produced and were co-eluting during the LC/MS analyses.     

Spatial and temporal trends in surface water and sediment contamination in the Laurentian Great Lakes

Data from recent sediment and surface water surveys have been collated and mapped to illustrate the spatial distribution of contaminants across the entire Great Lakes basin. Information from historical surveys, together with data from surface water monitoring programs in three major connecting channels, has also been collated in order to evaluate temporal trends. In general, Lakes Superior and Michigan exhibited the lowest levels of sediment contamination while Lake Ontario had the highest. Contaminants such as gamma-HCH (lindane) and dieldrin were ubiquitous in surface waters across the entire basin, which was indicative of atmospheric sources. The distribution of other compounds including hexachlorobenzene, octachlorostyrene and mirex indicated the presence of local sources within the watersheds of the connecting channels. Surficial sediment contamination was found to have decreased markedly since the late 1960s and 1970s. Similarly, surface water contamination decreased over the period 1986-1997 with concentrations of dieldrin, hexachlorobenzene, octachlorostyrene and mirex reduced by over 50%. However, the spatial distributions of both sediment and surface water contamination indicate that further effort is warranted in reducing local sources of contaminants, particularly in Lake Ontario.     

Prediction of two-phase capillary pressure-saturation relationships in fractional wettability systems

Capillary pressure/saturation data are often difficult and time consuming to measure, particularly for non-water-wetting porous media. Few capillary pressure/saturation predictive models, however, have been developed or verified for the range of wettability conditions that may be encountered in the natural subsurface. This work presents a new two-phase capillary pressure/saturation model for application to the prediction of primary drainage and imbibition relations in fractional wettability media. This new model is based upon an extension of Leverett scaling theory. Analysis of a series of DNAPL/water experiments, conducted for a number of water/intermediate and water/organic fractional wettability systems, reveals that previous models fail to predict observed behavior. The new Leverett–Cassie model, however, is demonstrated to provide good representations of these data, as well as those from two earlier fractional wettability studies. The Leverett–Cassie model holds promise for field application, based upon its foundation in fundamental scaling principles, its requirement for relatively few and physically based input parameters, and its applicability to a broad range of wetting conditions.     

Enantiomer fractions of chiral organochlorine pesticides and polychlorinated biphenyls in standard and certified reference materials

Enantiomeric ratios (ERs) and enantiomeric fractions (EFs) of a number of chiral organochlorine pesticides and PCB atropisomers were measured by chiral gas chromatography/mass spectrometry (GC/MS) in five standard (SRM) and certified (CRM) reference materials: SRM 1588a (organics in cod liver oil), SRM 1945 (organics in whale blubber), Marine Mammal Quality Assurance Exercise Control Material IV (NIST IV, organics in whale blubber), CRM trout, and CRM EC-5 (sediment). Target analytes were cis- and trans-chlordane, heptachlor exo-epoxide, oxychlordane, U82, MC5, MC6, MC7, o,p^′-DDT, and PCB congeners 91, 95, 136, 149, 174, 176, and 183. Measured ERs and EFs are in close agreement with the few literature values reported for some of these analytes in SRMs and CRMs. Chiral PCB ERs and EFs measured by one-dimensional chiral GC/MS were similar to values measured using multidimensional chiral GC/MS. Non-racemic chiral compositions are in agreement with known uptake and biotransformation in the respective environmental matrices. These values should aid in the quality assurance/quality control methodologies for chiral environmental chemistry using standardized reference materials.     

Perchlorate in water, soil, vegetation, and rodents collected from the Las Vegas Wash, Nevada, USA

Water, soil, vegetation, and rodents were collected from three areas along the Las Vegas Wash, a watershed heavily contaminated with perchlorate. Perchlorate was detected at elevated concentrations in water, soil, and vegetation, but was not frequently detected in rodent liver or kidney tissues. Broadleaf weeds contained the highest concentrations of perchlorate among all plant types examined. Perchlorate in rodent tissues and vegetation was correlated with perchlorate concentrations in soil as expected, however rodent residues were not highly correlated with plant perchlorate concentrations. This indicates that soil may be a greater source, or a more constant source of perchlorate exposure in rodents than vegetation.     

Deforestation alters phytotelm habitat availability and mosquito production in the Peruvian Amazon.

We quantified the effects of deforestation, and subsequent cultivation and forest regeneration, on the abundance and composition of mosquito larval habitats, specifically phytotelmata (plant-held waters), in the western Amazon basin. Recently deforested sites were characterized by increased phytotelm density (1.6 phytotelmata/m2) and greater relative abundance of fallen-plant-part phytotelmata (76%) compared to intact forests (0.9 phytotelmata/m2 and 25% fallen plant parts). As a result, the total volume of colonizable phytotelm water was significantly larger in new clearings. Subsequent cultivation of cleared land with mixed crops including pineapple and plantain had similar consequences: phytotelm density (2.2 units/m2) was significantly larger in plantations than in forests due to greater relative abundance of water-filled plant axils (71% vs. 39% in forest). Such axils are the preferred larval habitats for Wyeomyia spp. mosquitoes, which showed a similarly significant increase in production in plantations (0.25 larvae/m2) vs. forests (0.04 larvae/m2). Likewise, Limatus spp. mosquitoes were an order of magnitude more abundant in altered landscapes (especially in recently deforested and cultivated areas) than in mature forest, due to increased abundance of fallen-plant-part phytotelmata, in which they are typically the most common colonists. Because they are potential vectors of pathogens in a region of high endemic and emergent virus activity, increases in local abundance of Limatus spp. and Wyeomyia spp. due to large-scale deforestation and agriculture may influence rates of disease transmission.     

Sequential male mate choice in a fish,the Pacific blue-eye<Emphasis Type="Italic"> Pseudomugil signifer</Emphasis>

Mate choice is not just a female preoccupation. Under some circumstances, males may also be choosy. However, studies of male mate choice have generally been confined to situations where males can make direct comparisons between potential partners. In contrast, sequential male mate choice has largely been overlooked despite its biologically importance, especially if current investment in mate attraction diminishes a males future mating opportunities. Using the Pacific blue-eye fish Pseudomugil signifer, we show that males are capable of exercising sequential mate choice. When presented sequentially with large and small females, males spent more effort courting the former. However, males did not appear to modify the time spent courting a given female based on the size of the female encountered previously. We suggest that greater attention to the sequential choice problem in males may help illuminate similarities and differences between the sexes when it comes to mating decisions.Communicated by T. Czeschlik     

Play behavior and motor development in juvenile Belding’s ground squirrels (<Emphasis Type="Italic">Spermophilus beldingi</Emphasis>)

We evaluated the relationship between play behavior and motor development in juvenile Beldings ground squirrels (Spermophilus beldingi). We observed the social play behavior of juvenile S. beldingi during their primary play period and conducted motor skills tests at the beginning and end of the play period. We also placed different-sized boxes in juveniles natal areas during the play period and observed box climbing behavior to assess the difficulty of non-social play tasks undertaken by juveniles. Rates of social play were greater in heavy compared to light individuals, supporting the idea that juveniles must selectively allocate available energy among competing demands such as growth and play behavior. Juveniles played almost exclusively with littermates; however, they did not play at equal rates with all partners. Rather, they tended to have one preferred partner and to devote significantly less time to playing with each additional partner, indicating that stability and familiarity are important in social play interactions. Motor skill levels at the end of the play period were greater among juveniles who played with many compared to few partners, suggesting that exposure to a variety of play interactions helps facilitate motor development. Improvement in motor skills was greater among juveniles who played at high compared to low rates, had several compared to few male play partners, and engaged in several compared to few play bouts with male partners, suggesting that elements of play with male partners prominently influence motor development. The partner with whom males played at the highest rate tended to be male, and rates of social play were highest in male biased litters, raising the possibility that improvement in motor proficiency arising from play with males may be especially important for young males. The size of experimental boxes that juveniles climbed increased during the play period, supporting the idea that individuals choose play tasks that pose the greatest challenge.Communicated by T. Czeschlik     

Size-selective harvesting alters life histories of a temperate sex-changing fish.

Selective mortality, whether caused naturally by predation or through the influence of harvest practices, initiates changes within populations when individuals possessing certain heritable traits have increased fitness. Theory predicts that increased mortality rates will select for changes in a number of different life history characteristics. For example, fishing often targets larger individuals and has been shown repeatedly to alter population size structure and growth rates, and the timing of maturation. For sex-changing species, selective fishing practices can affect additional traits such as the mature population sex ratio and the timing of sexual transformation. Using historical comparisons, we examined the effects of exploitation on life history characteristics of California sheephead, Semicossyphus pulcher, a temperate protogynous (female-male sex changer) labrid that inhabits nearshore rocky environments from central California, USA, to southern Baja California, Mexico. Recreational fishing intensified and an unregulated commercial live-fish fishery developed rapidly in southern California between the historical and current studies. Collections of S. pulcher from three locations (Bahia Tortugas, Catalina Island, and San Nicolas Island) in 1998 were compared with data collected 20-30 years previously to ascertain fishery-induced changes in life history traits. At Bahia Tortugas, where fishing by the artisanal community remained light and annual survivorship stayed high, we observed no changes in size structure or shifts in the timing of maturation or the timing of sex change. In contrast, where recreational (Catalina) and commercial (San Nicolas) fishing intensified and annual survivorship correspondingly declined, males and females shifted significantly to smaller body sizes, females matured earlier and changed sex into males at both smaller sizes and younger ages and appeared to have a reduced maximum lifespan. Mature sex ratios (female:male) increased at San Nicolas, despite a twofold reduction in the mean time spent as a mature female. Proper fisheries management requires measures to prevent sex ratio skew, sperm limitation, and reproductive failure because populations of sequential hermaphrodites are more sensitive to size-selective harvest than separate-sex species. This is especially true for S. pulcher, where different segments of the fishery (commercial vs. recreational) selectively target distinct sizes and therefore sexes in different locations.     

Financing remediation by delisting and selling clean portions of affected property

It is an established fact that property owners can face significant liabilities as a result of an on-site environmental contamination problem. This paper outlines a successful, innovative remedial strategy that, in conjunction with agency negotiation, afforded a property owner minimal financial expenditure and, at the same time, facilitated property cleanup and reuse. The strategy includes the delisting and sale of “clean” portions of the property to obtain the finances necessary to remediate the remaining “impacted” portion of the property. Previous investigations performed by EPA indicate the affected area to be a five to seven acre area located in the northeast portion of the property. Since a portion of the property was affected, significant restrictions for long-term use were placed on the entire property. A summary of environmental data generated for the property was prepared and submitted to the agency. This data summary communicated a strategy which was developed to delist and sell the “clean” portion of the property and to use the proceeds to clean up the affected property. To accomplish this, several tasks were outlined, including work-plan preparation and submittal, data collection, and interim remedial activities. In addition, a risk assessment is planned to identify potential threats to receptors downgradient of the impacted areas. This strategy allows the owner of an environmentally distressed property to use financial assets of the property to facilitate an acceptable solution with both regulatory agencies and the surrounding community.