Nonlinear and competitive sorption of apolar compounds in black carbon-free natural organic materials

Numerous studies have reported a spectrum of sorption phenomena in soils, sediments, and organic matter isolates of those materials that are inconsistent with a partition model proposed in the late 1970s and early 1980s, a model predicated on a hypothesis that sorption is linear and noncompetitive. To explain these nonideal phenomena, prior studies have proposed a hard-soft (glassy-rubbery) model for SOM (soil and sediment organic matter), while others have attributed them singularly to BC (black carbon: soot and charcoal) particles present in topsoils and sediments. In this study, we demonstrated nonideal sorption behavior (isotherm nonlinearity, competitive effects) for a group of apolar compounds in a large set of natural and model organic materials, including a commercial lignin and humic acids from different sources. Complete oxidation of samples by an acidic dichromate method was taken to signify the absence of BC. (However, polymethylene units are stable even if functionalized on both ends, making the technique unreliable for quantifying BC.) Other samples were inferred free of BC by their source and method of preparation. Characterization by thermalanalytical methods indicated the glassy character of the organic materials. The origin of the nonideal behaviors appears to be the glassy character of these materials. Sorption nonlinearity increased or decreased by changing temperature, cosolvent content, or degree of cross-linking by metal ions as predicted for organic solids in a glassy state. We conclude that macromolecular humic substances in the environment may exhibit nonideal sorption behavior in soils and sediments, quite apart from any such behaviors attributable to BC.     

Baseline ambient gaseous ammonia concentrations in the Four Corners area and eastern Oklahoma, USA

Ambient ammonia monitoring using Ogawa passive samplers was conducted in the Four Corners area and eastern Oklahoma, USA during 2007. The resulting data will be useful in the multipollutant management of ozone, nitrogen oxides, and visibility (atmospheric regional haze) in the Four Corners area, an area with growing oil/gas production and increasing coal-based power plant construction. The passive monitoring data also add new ambient ammonia concentration information for the U.S. and will be useful to scientists involved in present and future visibility modeling exercises. Three week integrated passive ammonia samples were taken at five sites in the Four Corners area and two sites in eastern Oklahoma from December, 2006 through December, 2007 (January, 2008 for two sites). Results show significantly higher regional background ammonia concentrations in eastern Oklahoma (1.8 parts per billion (ppb) arithmetic mean) compared to the Four Corners area (0.2 ppb arithmetic mean). Annual mean ammonia concentrations for all Four Corners area sites for the 2007 study ranged from 0.2 ppb to 1.5 ppb. Peak ambient ammonia concentrations occurred in the spring and summer in both areas. The passive samplers deployed at the Stilwell, Oklahoma site compared favorably with other passive samplers and a continuous ammonia monitoring instrument.     

Efficiency assessment of Common Effluent Treatment Plant (CETP) treating tannery effluents

The efficacy of Common Effluent Treatment Plant (CETP) based on activated sludge process employed for treatment of tannery effluent was analyzed for the efficiency to reduce chromium and other contaminants. Physico-chemical parameters of treated effluent were found within permissible levels of statutory limits. A significant reduction in COD and BOD levels were achieved during the course of treatment in CETP. A reduction of 98.46%, 87.5%, and 96.15% in bacterial counts especially in pathogens like Escherichia coli, Vibrio spp., and Pseudomonas spp. were observed after treatment. Pathogens were not detected in the dried sludge. Complete elimination of fecal streptococci was observed in treated effluent. Around 10.8% of microbial isolates from the effluent showed ability to reduce chromate >90%. In treated effluent chromium level was 5.48 mg/L, which exceeds the statutory limit of Indian standards. Cleaner production options to reduce chromium levels before discharging into water bodies is discussed.     

Short-term variability of water quality and its implications on phytoplankton production in a tropical estuary (Cochin backwaters—India)

Changes in the phytoplankton biomass (chlorophyll a), production rate, and species composition were studied over two seasons using the time series measurements in the northern limb of the Cochin estuary in relation to the prevailing hydrological conditions. The present study showed the significant seasonal variation in water temperature (F = 69.4, P < 0.01), salinity (F = 341.93, P < 0.01), dissolved inorganic phosphorous (F = 17.71, P < 0.01), and silica (F = 898.1, P < 0.01) compared to nitrogen (F = 1.646, P > 0.05). The uneven input of ammonia (3.4–224.8 μM) from upstream (Periyar River) leads to the inconsistency in the N/P ratio (range 6.8–262). A distinct seasonality was observed in Si/N (F = 382.9, P < 0.01) and Si/P (F = 290.3, P < 0.01) ratios compared to the N/P ratio (F = 1.646, P > 0.05). The substantial increase in chlorophyll a (average, 34.8 ± 10 mg m^???3) and primary production (average, 1,304 ± 694 mg C m^???3 day^???1) indicated the mesotrophic condition of the study area during the premonsoon (PRM) and it was attributed to the large increase in the population of nanoplankton (size < 20 μ ) such as Skeletonema costatum, Thalassiosira subtilis, Nitzschia closterium, and Navicula directa. In contrast, during the post monsoon (PM), low chlorophyll a concentration (average, 9.3 ± 9.2 mg m^???3) and primary production (average, 124 ± 219 mg C m^???3 day^???1) showed heterotrophic condition. It can be stated that favorable environmental conditions (optimum nutrients and light intensity) prevailing during the PRM have enhanced the abundance of the nanoplankton community in the estuary, whereas during the PM, the light limitation due to high turbidity can reduce the nanoplankton growth and abundance, even though high nutrient level exists.     

Impacts of climate-induced changes on the distribution of pesticides residues in water and sediment of Lake Naivasha, Kenya

This study reports evidence of increased chlorpyrifos contamination in sediment and water in Lake Naivasha following its intensive application in the horticultural farms in the catchment area. Analytical results show that levels of chlorpyrifos residues were influenced by climate-induced rainfall pattern with higher levels reported during period of heavy precipitation with significant decrease during low rainfall. On average, the levels ranged between 14.8 and 32.8 ng g^?1 in sediment during rainy season compared to a range of 8.5–16.6 ng g^?1 in the dry season. Additionally, the mean concentration of chlorpyrifos in water ranged between 8.61 and 22.4 μg L^?1 during rainy season and below detection limit (bdl) ?13.6 μg L^?1 in dry season as quantified by enzyme-linked immunosorbent assay. Meanwhile, independent t test analysis indicated that there was significant difference in concentration at p?≤?0.05 between the seasons with respect to sediment and water samples. This demonstrated that climate-induced variations had considerable influence on contamination. While diazinon and carbofuran were equally applied intensively, their levels were below the detection limit in the all the samples analyzed. ELISA results were validated by the capillary-HPLC photodiode-array detector instrument analysis, and statistical comparison showed no significant difference between them. It was evident that chlorpyrifos residues determination in water and sediment by ELISA can be a useful strategy in environmental management and monitoring program, and a complimentary analytical tool to high performance liquid chromatography. Levels of chlorpyrifos detected in sediment and water were found to exceed recommended criteria for protection of aquatic life and preservation of water quality and may be hazardous if not regularly monitored.     

Histopathology alterations and lipid peroxidation as biomarkers of hydrocarbon-induced stress in earthworm, Eudrilus eugeniae

This study investigated the biomarker responses of the earthworm, Eudrilus eugeniae, exposed to sublethal concentrations of benzene, toluene and xylene (BTX) for a time span of 28 days. Lipid peroxidation (LPO) and histopathological alterations were examined. Toxicological evaluations of BTX were carried out against E. eugeniae. On the basis of the 96-h LC₅₀ value, xylene (1.212 mg/kg) was found to be the most toxic followed by toluene (1.335 mg/kg) and benzene (1.896 mg/kg) was the least toxic. The exposure of earthworms to sublethal concentrations (1/10th and 1/100th of 96 h LC₅₀) of BTX premixed with the substrate (loamy and humus soil) induced pathological changes in the clitella such as severe lesion, necrosis and dark brown pigments. The result of the lipid peroxidation assay showed a significant increase in oxidative damage with LPO values ranging from 2.58–7.8 nM/g in exposed animals when compared to 0.07 nM/g in the control group. The findings from this study suggest the use of LPO and histopathology as useful biomarkers of exposure for early detection of petroleum related stress in terrestrial ecosystems     

Microbial activity and carbon, nitrogen, and phosphorus content in a subtropical seagrass estuary (Florida Bay): evidence for limited bacterial use of seagrass production

Bacterial abundance, production, and extracellular enzyme activity were determined in the shallow water column, in the epiphytic community of Thalassia testudinum, and at the sediment surface along with total carbon, nitrogen, and phosphorus in Florida Bay, a subtropical seagrass estuary. Data were statistically reduced by principle components analysis (PCA) and multidimensional scaling and related to T. testudinum leaf total phosphorus content and phytoplankton biomass. Each zone (i.e., pelagic, epiphytic, and surface sediment community) was significantly dissimilar to each other (Global R = 0.65). Pelagic aminopeptidase and sum of carbon hydrolytic enzyme (esterase, peptidase, and α- and β-glucosidase) activities ranged from 8 to 284 mg N m⁻² day⁻¹ and 113–1,671 mg C m⁻² day⁻¹, respectively, and were 1–3 orders of magnitude higher than epiphytic and sediment surface activities. Due to the phosphorus-limited nature of Florida Bay, alkaline phosphatase activity was similar between pelagic (51–710 mg P m⁻² day⁻¹) and sediment (77–224 mg P m⁻² day⁻¹) zones but lower in the epiphytes (1.1–5.2 mg P m⁻² day⁻¹). Total (and/or organic) C (111–311 g C m⁻²), N (9.4–27.2 g N m⁻²), and P (212–1,623 mg P m⁻²) content were the highest in the sediment surface and typically the lowest in the seagrass epiphytes, ranging from 0.6 to 8.7 g C m⁻², 0.02–0.99 g N m⁻², and 0.5–43.5 mg P m⁻². Unlike nutrient content and enzyme activities, bacterial production was highest in the epiphytes (8.0–235.1 mg C m⁻² day⁻¹) and sediment surface (11.5–233.2 mg C m⁻² day⁻¹) and low in the water column (1.6–85.6 mg C m⁻² day⁻¹). At an assumed 50% bacterial growth efficiency, for example, extracellular enzyme hydrolysis could supply 1.8 and 69% of epiphytic and sediment bacteria carbon demand, respectively, while pelagic bacteria could fulfill their carbon demand completely by enzyme-hydrolyzable organic matter. Similarly, previously measured T. testudinum extracellular photosynthetic carbon exudation rates could not satisfy epiphytic and sediment surface bacterial carbon demand, suggesting that epiphytic algae and microphytobenthos might provide usable substrates to support high benthic bacterial production rates. PCA revealed that T. testudinum nutrient content was related positively to epiphytic nutrient content and carbon hydrolase activity in the sediment, but unrelated to pelagic variables. Phytoplankton biomass correlated positively with all pelagic components and sediment aminopeptidase activity but negatively with epiphytic alkaline phosphatase activity. In conclusion, seagrass production and nutrient content was unrelated to pelagic bacteria activity, but did influence extracellular enzyme hydrolysis at the sediment surface and in the epiphytes. This study suggests that seagrass-derived organic matter is of secondary importance in Florida Bay and that bacteria rely primarily on algal/cyanobacteria production. Pelagic bacteria seem coupled to phytoplankton, while the benthic community appears supported by epiphytic and/or microphytobenthos production.     

Helpers and egg investment in the cooperatively breeding acorn woodpecker: testing the concealed helper effects hypothesis

In cooperatively breeding acorn woodpeckers (Melanerpes formicivorus), helper males have a large positive effect on fledging success in good acorn crop years but only a small positive effect in poor acorn crop years, while helper females exhibit the opposite pattern. Based on these findings, we tested the “concealed helper effects” hypothesis, which proposes that laying females reduce investment in eggs (with respect to their size, number, or quality) in a way that confounds helper effects and results in an absence of a relationship between helpers and breeding success. Results generally failed to support the hypothesis. Mean egg size was positively related to temperatures during the 10 days prior to egg-laying and negatively related to the food supply as indexed by the prior fall’s acorn crop, but there were no significant differences vis-à-vis helpers except for interactions with the acorn crop that only partly corresponded to those predicted. With respect to clutch size, females laid larger clutches when assisted by female helpers, opposite the pattern predicted. Although our results suggest that egg size is adjusted to particular ecological circumstances, we conclude that neither egg nor clutch size is adjusted in a way that confounds the apparent effects of helpers, as proposed by the concealed helper effects hypothesis.