Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

Minimizing life-cycle costs of gun propellant selection through model-based decision making: a case study in environmental screening and performance testing

The work presented here demonstrates the first phases of a newly-proposed gun propellant formulation process that will minimize life-cycle costs through science-based design. This new approach to gun propellant formulation proposes maximal use of modeling and simulation in the earliest phases of the developmental cycle to screen candidate formulations, resulting in the elimination of probable poor performers and the identification of the most promising candidates for further study and testing. The screening and identification of promising candidate formulations is demonstrated in the study presented here under the assumption of a specific weapon platform and user requirements. The process of selecting a propellant for the assumed gun system application has been distilled into a series of measurable steps leading from a set of candidate materials, through logical and numerical filters, to a shorter list of energetic materials demonstrated as viable choices for the weapon platform. Environmental filtering and performance modeling are used to screen propellants through a well-defined sequence of tests designed to weed out materials that do not meet standards in terms of safety, energy, or manufacturability. Because much of the testing is performed by computer modeling, the gun systems and energetic materials need not be present (nor even existent) in order to be described and matched against performance requirements for future applications. The calculations presented here demonstrate that utilizing computer models in the early developmental stages of the formulation process rather than physical testing produces enormous savings in labor, material, and environmental costs, along with a tremendous reduction in the time required to select a "best candidate" propellant.     

Formation of bound residues by naphthalene and cis-naphthalene-1,2-dihydrodiol

The formation of bound residues by naphthalene and its metabolite, cis-naphthalene-1,2-dihydrodiol, in a sediment (1% OC), a silty loam soil (2.9% OC) and a peat (26% OC) was examined. The experiments were carried out under both sterile and nonsterile conditions for up to 35 days. The samples containing bound contaminant were hydrolyzed at an alkaline pH and fractionated using 3,000 and 500 Da molecular weight cutoff ultrafiltration membranes in series. The results for all the geosorbents examined showed that bound residue formation is low for naphthalene and between 5 and 20 times higher for the metabolite. The amount of bound residues released by hydrolysis was higher for the metabolite than for the parent compound for all the samples. The molecular weight distribution of bound radioactivity after hydrolysis showed binding to the high molecular weight components of the sediment organic matter and to the low molecular weight components for soil and peat organic matter when incubated with cis-naphthalene-1,2-dihydrodiol. Experiments performed with naphthalene-UL-(14)C showed larger amounts of bound residue found than in experiments with naphthalene-1-(14)C.     

Runoff loss of pesticides and soil: a comparison between vegetative mulch and plastic mulch in vegetable production systems

Current vegetable production systems use polyethylene (plastic) mulch and require multiple applications of agrochemicals. During rain events, runoff from vegetable production is enhanced because 50 to 75% of the field is covered with an impervious surface. This study was conducted to quantify off-site movement of soil and pesticides with runoff from tomato (Lycopersicon esculentum Mill.) plots containing polyethylene mulch and a vegetative mulch, hairy vetch (Vicia villosa Roth). Side-by-side field plots were instrumented with automated flow meters and samplers to measure and collect runoff, which was filtered, extracted, and analyzed to determine soil and pesticide loss. Seasonal losses of two to four times more water and at least three times as much sediment were observed from plots with polyethvlene mulch (55.4 to 146 L m(-2) and 247 to 535 g m(-2), respectively) versus plots with hairy vetch residue (13.7 to 75.7 L m(-2) and 32.8 to 118 g m(-2), respectively). Geometric means (+/-standard deviation) of total pesticide loads for chlorothalonil (tetrachloroisophthalonitrile) and alpha-and beta-endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro6,9-methano-2,4,3-benzodioxathiepin 3-oxide) for a runoff event were 19, 6, and 9 times greater from polyethylene (800+/-4.6, 17.6+/-3.9, and 39.1+/-4.9 microg m(-2), respectively) than from hairy vetch mulch plots (42+/-6.0, 2.8+/-5.0, and 4.3+/-4.6 microg m(-2), respectively) due to greater concentrations and larger runoff volumes. The increased runoff volume, soil loss, and off-site loading of pesticides measured in runoff from the polyethylene mulch suggests that this management practice is less sustainable and may have a harmful effect on the environment.     

Impact of cocoa agricultural intensification on bird diversity and community composition

To meet the growing demand for chocolate, cocoa (Theobroma cacao) agriculture is expanding and intensifying. Although this threatens tropical forests, cocoa sustainability initiatives largely overlook biodiversity conservation. To inform these initiatives, we analyzed how cocoa agriculture affects bird diversity at farm and landscape scales with a meta-analysis of 23 studies. We extracted 214 Hedges' g* comparisons of bird diversity and 14 comparisons of community similarity between a forest baseline and 4 farming systems that cover an intensification gradient in landscapes with high and low forest cover, and we summarized 119 correlations between cocoa farm features and bird diversity. Bird diversity declined sharply in low shade cocoa. Cocoa with >30% canopy cover from diverse trees retained bird diversity similar to nearby primary or mature secondary forest but held a different community of birds. Diversity of endemic species, frugivores, and insectivores (agriculture avoiders) declined, whereas diversity of habitat generalists, migrants, nectarivores, and granivores (agriculture associates) increased. As forest decreased on the landscape, the difference in bird community composition between forest and cocoa also decreased, indicating agriculture associates replaced agriculture avoiders in forest patches. Our results emphasize the need to conserve forested landscapes (land sparing) and invest in mixed-shade agroforestry (land sharing) because each strategy benefits a diverse and distinct biological community.     

Age and growth rates of Hawaiian hawksbill turtles (Eretmochelys imbricata) using skeletochronology

The Hawaiian hawksbill population has fewer than 20 females nesting per year; hence, there is a need to monitor this population closely and basic biological information on individual growth and age to maturity is critical. We present a skeletochronology analysis of Hawaiian hawksbills using humeri recovered from 30 dead stranded hawksbills, plus 10 dead hatchlings. Growth mark morphology shows readily distinguishable marks similar in appearance to other species, though some animals displayed more diffuse marks. Growth rates remained high (average 2.24–4.77 cm year^?1) from 20 to 80 cm straight carapace length (SCL). Hawksbills larger than 80 cm SCL had average growth rates of 0.3 cm year^?1. There were few adult turtles in the sample; however, results indicate hawksbills have faster growth rates than loggerhead or green turtles, with probable average age to maturity (at size 78.6 cm SCL) occurring between 17 and 22 years.     

Dietary constraints on reproductive periodicity in two sympatric deep-sea astropectinid seastars

Examination of the diet of two sympatric species of seastar, Bathybiaster vexillifer and Plutonaster bifrons from 2200 m depth in the Rockall Trough, NE Atlantic Ocean (57°18'N; 10°28'W), suggested that diet may determine the different reproductive patterns found between these two species. In the non-seasonally breeding B. vexillifier, the diet showed a high Shannon-Wiener prey diversity index, the dominant prey being the irregular echinoid Hemiaster expergitus together with a variety of prosobranch gastropods and protobranch bivalves. By contrast, the prey diversity in the seasonally breeding P. bifrons was significantly lower than that of B. vexillifer. In addition, organic carbon content in the sediment residue in the stomachs of P. bifrons displayed a seasonal cycle, while no such seasonality was detected in B. vexillifer. The stomachs of P. bifrons also contained a higher proportion of scavenged material, including the seasonally available remains of mesopelagic blue whiting. These data, together with Bathysnap (time-lapse camera) observations of feeding behaviour in both species, suggest that B. vexillifer is a predator feeding deep in the sediment, whereas P. bifrons feeds close to the sediment surface where it is affected by the seasonal availability of phytodetritus and fish carcasses.     

Variation in resource availability changes the impact of invasive thistles on native bunchgrasses.

The threat posed by invasive nonnative plants to native plant populations is one of the largest challenges facing both conservation biology and restoration ecology. California has been highly impacted by invaders, although many relict stands of native plants are found on shallow, rocky soils with limited resources. The abiotic conditions of these sites may strongly influence the performance of an invasive plant and its effect on resident native species. In addition, the maturity of native plants in these sites may modulate an invader's impact; larger, well-established plants may be better able to resist invaders. In this study we examined how the impact of an invasive thistle (Centaurea solstitialis) on a native perennial bunchgrass (Nassella pulchra) changed in response to variation in soil depth, soil water availability, and bunchgrass maturity. We measured plant performance in terms of survival, growth, reproduction, and predawn water potential. We found that soil depth, water availability, and bunchgrass maturity acted in concert to influence the impact of the invasive thistle on the native bunchgrass. Both species performed better in deep soils, especially during dry years. The combination of shallow soil and low water availability reduced C. solstitialis performance and ameliorated its negative effect on N. pulchra growth and reproduction. Higher water availability resulted in a stronger negative effect of C. solstitialis on N. pulchra in both shallow and deep soils. However, as N. pulchra matured and increased in size, we saw a steady decline in C. solstitialis growth and reproductive output. Higher water availability increased the performance of C. solstitialis in shallow soils. C. solstitialis may thus have a stronger impact on N. pulchra and be more able to invade relict stands of N. pulchra in shallow soils during high-rainfall years. However, established stands of N. pulchra appear to be more resistant to invasion by C. solstitialis as N. pulchra plants grow older and larger.