Biodegradability testing of synthetic ester lubricants--effects of additives and usage

The optimised biodegradability test system "O2/CO2 Headspace Test with GC-TCD" is used for the assessment of synthetic ester lubricants. The effects of both additives and usage on biodegradability are examined and discussed. Ester based cutting fluids and hydraulic fluids with and without additives are used under defined conditions at machine tools and hydraulic and plain bearing test benches. The lubricants are characterised additionally with respect to kinematic viscosity, acidity and elemental composition. Furthermore, a formulated mineral oil is characterised before and after usage at an hydraulic test bench. The results clearly show that the mineral oil is far less biodegradable than the ester oils and that their biodegradability is not affected by usage. Biodegradability of the ester oils is mainly depending on the characteristics of the base fluids and not affected by the additives. Antioxidants are influencing stability respectively biodegradability indirectly, since they prevent oxopolymerisation effects. Other effects of usage on biodegradation are not detected. In this context, the antioxidants ensure ready biodegradability and have a positive effect on the environmental fate of synthetic ester lubricants.     

Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.     

Living with a large reduction in permited loading by using a hydrograph-controlled release scheme

The Total Maximum Daily Load (TMDL) for ammonia and biochemical oxygen demand for the Pee Dee, Waccamaw, and Atlantic Intracoastal Waterway system near Myrtle Beach, South Carolina, mandated a 60-percent reduction in point-source loading. For waters with a naturally low background dissolved-oxygen concentrations, South Carolina anti-degradation rules in the water-quality regulations allows a permitted discharger a reduction of dissolved oxygen of 0.1 milligrams per liter (mg/L). This is known as the 0.1 rule. Permitted dischargers within this region of the State operate under the 0.1 rule and cannot cause a cumulative impact greater than 0.1 mg/L on dissolved-oxygen concentrations. For municipal water-reclamation facilities to serve the rapidly growing resort and retirement community near Myrtle Beach, a variable loading scheme was developed to allow dischargers to utilize increased assimilative capacity during higher streamflow conditions while still meeting the requirements of a recently established TMDL.As part of the TMDL development, an extensive real-time data-collection network was established in the lower Waccamaw and Pee Dee River watershed where continuous measurements of streamflow, water level, dissolved oxygen, temperature, and specific conductance are collected. In addition, the dynamic BRANCH/BLTM models were calibrated and validated to simulate the water quality and tidal dynamics of the system. The assimilative capacities for various streamflows were also analyzed.The variable-loading scheme established total loadings for three streamflow levels. Model simulations show the results from the additional loading to be less than a 0.1mg/L reduction in dissolved oxygen. As part of the loading scheme, the real-time network was redesigned to monitor streamflow entering the study area and water-quality conditions in the location of dissolved-oxygen sags. The study reveals how one group of permit holders used a variable-loading scheme to implement restrictive permit limits without experiencing prohibitive capital expenditures or initiating a lengthy appeals process.     

Biodegradation of low aqueous concentration pentachlorophenol (PCP) contaminated groundwater

Bioremedial treatment to remove low level organic contamination to regulatory standards has met with limited success. In this study source water from a contaminated surficial aquifer at a former wood treatment facility was used to evaluate the potential for indigenous microorganisms to degrade low level (< 1.0 mg) pentachlorophenol (PCP) to a regulatory drinking water standard of 0.001 mg/L. PCP degradation was evaluated in series of batch reactors in a two phase study to (a) determine the rate and extent of PCP removal and (b) evaluate the impact of nutrient amendment (N and P) on removal rate. All reactors with the exception of the abiotic control demonstrated PCP removal to a level < 0.002 mg/L within a maximum period of 32 d with and without nutrient amendment. A regression analysis of reactive phosphate (ortho-P) concentration versus removal rate produced an R2 of 0.94 (p = 0.006) indicating a significant correlation between the level of available phosphate and PCP degradation rate. Selective bacterial enumeration (for PCP degrading bacteria) revealed PCP-degrading bacteria increased in abundance prior to and in conjunction with the degradation phase to a density of between 10(3) to 10(4) CFU/ml. Isolates were also analyzed for total fatty acids using Fatty Acid Methyl Ester (FAME) methodology and the results indicated that PCP degrading bacteria were present in the aquifer and consisted of predominately fluorescent, oxidase positive Pseudomonas species. Overall, data indicate that autochthonous microbes are capable of removing low level PCP (< 1.0 mg/L) to approach if not reach the regulatory standard of 0.001 mg/L with the addition of oxygen, with or without nutrient amendment. Results of this research can be applied to full-scale implementation of in-situ or ex-situ bioremediation of groundwater at former wood treatment facilities.     

Nutrients on Asphalt Parking Surfaces in an Urban Environment

Amounts of readily soluble nutrients on asphalt parking lot surfaceswere measured at four locations in metropolitan Phoenix, Arizona, U.S.A. Using a rainfall simulator, short intense rainfall events were generated to simulate `first flush' runoff. Samples were collected from 0.3 m² sections of asphalt at 8 to 10 sites on each of four parkinglots, during the pre-monsoon season in June-July 1998 and analyzed for dissolved NO₃ ^--N, NH₄ ⁺-N, soluble reactive phosphate (SRP), and dissolved organic carbon (DOC). Runoff concentrations varied considerably for NO₃ ^--N and NH₄ ⁺-N (between 0.1 and 115.8 mg L^-1) and DOC (26.1 to 295.7 mg L^-1), but less so for SRP (0.1 to 1.0 mg L^-1), representing average surface loadings of 191.3, 532.2, and 1.8 mg m^-2 respectively. Compared with similar data collected from undeveloped desert soil surfaces outside the city, loadings of NO₃ ^--N and NH₄ ⁺-N on asphalt surfaces were greater by factors of 91 and 13, respectively. In contrast, SRP loads showed little difference between asphalt and desert surfaces. Nutrient fluxes in runoff from a storm that occurred shortly after the experiments were used to estimate input-output budgets for 3 of the lots under study. Measured outputs of DOC and SRP were similar to those predicted using rainfall and experimentally determined surface loadings, but for NH₄ ⁺-N and particularly for NO₃ ^--N, estimated rainfall inputs and surface runoff were significantly higher than exports in runoff. This suggests that parking lots may be important sites for nutrient accumulation and temporary storage in arid urban catchments.