Microscale analytical methods for the quantitative detection of PCBs and PAHs in small tissue masses

Microscale methods (MM) were evaluated and compared to traditional methods (TM) for measuring polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in spiked and standard reference fish and mussel tissues. MMs are advantageous because they use small tissue masses (ca. 100 mg), and maintain sensitivity through reducing final extract volume (traditionally 1 ml) by an order of magnitude or more (40 μl—PCBs; 100 μl—PAHs). Procedural losses occurred in the MMs’ combined cleanup/primary evaporation step (19% PAHs; 6% PCBs), and the final extract concentration (14% PAHs; 22% PCBs). The PAH MM performed comparably to the TM. Although most PCBs had recoveries >50%, the PCB MM generally yielded lower recoveries than the TM. Average method detection limits were 0.6 μg/kg (TM) and 1.0 μg/kg (MM) for PCBs and 25.7 μg/kg (TM) and 27.7 μg/kg (MM) for PAHs. MMs described for PCB and PAH tissue samples are potentially viable alternatives to TMs, and could lead to cost savings in bioaccumulation/toxicity tests.     

Manure management effects on grass production, nutritive content, and soil nitrogen for a grass silage-based dairy farm

Legislation in the United States has recently focused on improving water quality by establishing management practices that limit the quantities of nutrients entering the water supply. Timely application and quantification of the amount of manure applied throughout the grass-growing season can reduce the loss of nutrients into ground or surface water while improving the quality and quantity of grass harvested. During the 2001 and 2002 growing seasons, we measured the effects of different manure application rates on grass yields, grass nutritive value, and soil chemistry on a dairy farm. On-farm estimates of manure N were combined with yield estimates and forage quality measures to evaluate the effects of varying levels of manure application. Yield estimates, N content of grass, and the amount of N in soil and manure were monitored at each cutting for plots amended at different manure application rates. There are three major outcomes of this evaluation: (i) new grass seedings were at higher risk of elevated levels of nitrate N in forage; (ii) increased forage nitrate N at harvest was associated with malfermented silage and increased levels of ammonia N, which resulted in less efficient use of metabolizable protein for milk production; and (iii) increased understanding of N cycling between manure, soil, and plant provided an opportunity to reduce purchased fertilizer.     

ENVIRONMENTAL IMPACTS OF APPLYING MANURE,FERTILIZER, AND SEWAGE BIOSOLIDS ON A DAIRY FARM1

ABSTRACT: Farms that once spread only manures are now also applying sewage biosolids (sludge) and/or other wastes such as those from food processing. The objective of this study was to monitor environmental impacts at a dairy farm applying these materials. Fields were selected representing recent waste applications of manure (M1, M2), sewage biosolids (B1, B2), or fertilizer only control (F1, F2), although most fields had historical biosolids applications. Fields representing each treatment were not experimental replicates because of varying applications and soil characteristics. Septage and food processing wastes were also applied. Soil percolates were collected with wick lysimeters. Runoff was sampled at seven stream sites. Test field soils and alfalfa (Medicago sativa) were analyzed for trace elements. Cumulative trace metal loadings were low, at most only 1 percent of USEPA Part 503 limits. Surface soil enrichment was most evident for Mo, P, and S. Alfalfa tissue showed no trends of concern. The B2 site had the greatest percolate concentrations for 6 of 13 elements. Percolate Cu was somewhat elevated at Sites M1, M2, B2, and Fl. Percolate sodium was elevated on all M and B fields and sulfur was greatest at M2, B1, and B2. Soluble orthophosphate correlated with stream discharge during intensive monitoring of Stream Sites S1 (fertilizer) and S2 (biosolids). Peaks in S2 streamwater Mo lagged large runoff events by five days. Total streamwater export of Cu, Na, Mo, and soluble P were greater from the S2 biosolids subwatershed than from the S1 fertilizer subwatershed. Percolate concentrations exceeded corresponding streamwater concentrations in most cases.     

Simultaneous monitoring of atmospheric methane and speciated non-methane hydrocarbon concentrations using Peltier effect sub-ambient pre-concentration and gas chromatography

Sub-ambient trapping, used to pre-concentrate atmospheric samples for non-methane hydrocarbon (NMHC) analysis by gas chromatography, can also be used to measure ambient methane concentrations. Above a sample volume of 40 ml, a dynamic equilibrium is established between ambient and trapped methane allowing for simultaneous quantitative determinations of methane and NMHC. The temperature stability of the trap is critical for quantitative methane analysis and this can be achieved by Peltier effect cooling. Simultaneous measurements of methane and NMHC reduce the equipment required for field trips and can ease the interpretation and modelling of atmospheric data. The feasibility for deployment of the system in remote locations was demonstrated by running the apparatus virtually unattended for a 5-day period. The correlations between the concentrations of methane, ethane and ethene measured during this period are discussed.     

A comparison of Lowry,Bradford and Smith protein assays using different protein standards and protein isolated from the marine diatom Thalassiosira pseudonana

Two spectrophotometric assays for protein commonly used in marine research (Coomassie stain, Bradford; alkaline copper, Lowry) and a more recent assay which has not been applied in this field (bicinchoninic acid, Smith) were compared for homogenates of the marine diatom Thalassiosira pseudonona using bovine serum albumin (BSA) as a standard. When homogenates were prepared by precipitating protein with trichloroacetic acid (TCA) and redissolving in 1 N NaOH, the protein content estimated by the Lowry and Smith assays agreed closely, but was consistently 20% higher than that indicated by the Bradford assay. To determine if this difference was due to the choice of a protein standard, protein from T. pseudonana was purified and compared to BSA, bovine gamma-globulin (BGG), and casein. The reactivity of the purified protein (expressed as the slope of the absorbance vs protein concentration curve) did not differ between cultures grown at high or low irradiance. For the Smith and Bradford assays the reactivity of BSA was not significantly different from algal protein, but for the Lowry assay, algal protein was significantly higher in reactivity than BSA. BGG was not significantly different in reactivity from algal protein for the Lowry and Smith assays, but BGG gave significantly lower absorbances than algal protein in the Bradford assay. These results suggest that BSA is a suitable standard for algal protein in the Bradford assays, while BGG is preferable for the Lowry assay. Either protein standard could be used for the Smith assay. Differences in purified algal protein reactivity compared to BSA could not account for the differences among the assays, nor could interference by chlorophyll a. Precipitating protein with TCA prior to analyses gave lower protein than direct analyses of homogenates for the Lowry and Smith assays, but no differences were found for the Bradford assay. As a result, the Lowry and Smith assays indicated up to 60% greater protein than the Bradford if TCA precipitation was not performed. This may be due to removal of free amino acids and small peptides which are less reactive in the Bradford assay. The 20% higher protein found in the Lowry or Smith vs Bradford assays may be due to different assay sensitivity to small peptides or other compounds which are precipitated along with proteins by TCA. Although the Smith assay is substantially simpler to perform than the Lowry, there appear to be no quantitative differences in the results. It remains unclear which spectrophotometric assay is most accurate, but the Bradford assay is faster and simpler, and is less likely to be affected by non-protein compounds found in marine phytoplankton.     

The influence of irradiance on the biochemical composition of three phytoplankton species and their nutritional value for larvae of the Pacific Oyster (Crassostrea gigas)

Three species of phytoplankton grown at high (HL) or low light (LL) were fed as saturating rations to laboratory-reared larval Crassostrea gigas. Larval C. gigas fed diets of HL grown Chaetoceros gracilis and HL grown Isochrysis aff. galbana grew faster than those fed LL grown cells of the same phytoplankton species. Faster growth of C. gigas larvae was consistently associated with increases in the percent composition of short chain saturated fatty acids (FA) 14:0+16:0 in the HL grown cells. There were no consistent and significant differences between HL and LL grown phytoplankton cells in their content of carbon, nitrogen, protein, lipid or carbohydrate. Intraspecific increases in percent composition of essential fatty acids (EFAs), 20:53 and 22:63, in the phytoplankton were not associated with improvements in the growth or survival of the oyster larvae. Oyster larvae fed diets of Phaeodactylum tricornutum with a relatively high proportion of EFAs grew more slowly than those fed C. gracilis. In this experiment the proportion of dietary EFA 20:53 was negatively correlated with oyster growth rates. The faster growing oyster larvae contained relatively more of the FAs 14:0+16:0 which may be useful as measures of larval oyster condition. After a diet of one phytoplankton species for ca. 10 d, oyster larvae acquired distinctive FA profiles resembling that of their phytoplankton prey.     

Climatic Variation and Solute Concentration and Flux in Meltwaters Draining from an Alpine Glacier

Measurements of electrical conductivity and discharge ofmeltwaters in the Gornera, which drains from the 83%glacierised basin containing Gornergletscher, PennineAlps, Switzerland, were undertaken between May andSeptember in both 1979 and 1998. Discharge in theGornera was 43% higher in 1998, average air temperatureduring the ablation season being 2.1 °C warmer andpreceding winter precipitation 28% lower than in 1979. Mean electrical conductivity of meltwater in 1998 wasreduced by 40%. In the same 60 day period in 1998,however, solute flux was augmented by only 2% bycomparison with 1979. Year-to-year climatic variations,reflected in discharge variability, strongly affectsolute concentration in glacial meltwaters, but havelimited impact on solute flux. Climatic conditionstranslate into meltwater quality through inter-relationships between mineral reaction rates, subglacialresidence time in contact with sediment, and discharge. Annual variability in solute flux depends on the extentto which volume of flow can offset decline in soluteconcentration brought about by reducing residence time.     

Glacier protection laws: Potential conflicts in managing glacial hazards and adapting to climate change

The environmental, socioeconomic and cultural significance of glaciers has motivated several countries to regulate activities on glaciers and glacierized surroundings. However, laws written to specifically protect mountain glaciers have only recently been considered within national political agendas. Glacier Protection Laws (GPLs) originate in countries where mining has damaged glaciers and have been adopted with the aim of protecting the cryosphere from harmful activities. Here, we analyze GPLs in Argentina (approved) and Chile (under discussion) to identify potential environmental conflicts arising from law restrictions and omissions. We conclude that GPLs overlook the dynamics of glaciers and could prevent or delay actions needed to mitigate glacial hazards (e.g. artificial drainage of glacial lakes) thus placing populations at risk. Furthermore, GPL restrictions could hinder strategies (e.g. use of glacial lakes as reservoirs) to mitigate adverse impacts of climate change. Arguably, more flexible GPLs are needed to protect us from the changing cryosphere.     

An analysis of spatial and temporal properties of daily sulfate, nitrate and chloride concentrations at UK urban and rural sites

Daily measurements of sulfate, nitrate and chloride in PM(10) have been made at three geographically separated UK sites over a three year period. Chloride shows a clear seasonal pattern with highest concentrations in winter, whilst sulfate and nitrate both show highest concentrations in the spring, apparently related to weather patterns. Spatial variability of both sulfate and nitrate is low in comparison to temporal variations, with high correlations of both species between all three sites, London (North Kensington), Harwell and Belfast, despite a geographic separation of 510 km. Both SO/SO(2) and NO/NO(x) ratios are considerably higher in summer than winter, reflecting a greater oxidising capacity of the atmosphere. SO(4)(2-)/NO(3)(-) ratios are higher in summer than winter, suggesting that aqueous phase oxidation of SO(2), expected to be most important in the winter months is not appreciably influencing production of sulfate aerosol, although greater dissociation of ammonium nitrate in summer may also play a role. Regression of concentrations at London, North Kensington with those from the proximate rural site of Harwell is interpreted as showing a similar effect of regional transport at the two sites and a small influence of local formation in the urban atmosphere or primary emissions, averaging 0.46 microg m(-3) of nitrate and 0.22 microg m(-3) of sulfate.