Aquatic toxicity structure-activity relationships for the zwitterionic surfactant alkyl dimethyl amine oxide to several aquatic species and a resulting species sensitivity distribution.

Amine oxide (AO) is a cationically charged surfactant at environmental pH and has previously been assessed in the OECD (Organization for Economic Cooperation and Development) High Production Volume (HPV) chemicals program. Typical of cationic chemicals, AO is highly aquatically toxic. In this study we vastly improve the knowledge of AO toxicity by developing acute Quantitative Structure Activity Relationships (QSARs) for an alga (Desmodesmus subspicatus), an invertebrate (Daphnia magna) and a fish (Danio rerio) using the appropriate array of OECD Test Guidelines. A chronic toxicity QSAR was also determined for the most sensitive taxon, Desmodesmus. Pure AO spanning the chain lengths of C8 to C16 were tested individually with trace analytical confirmation of exposures in all tests. The QSARs were all of high quality (R2 0.92-0.98) with slopes ranging from -0.338 to -0.484. QSARs were then used to normalize toxicity outcomes for a larger, previously published data set used in HPV, European REACH (Registration, Evaluation, and Authorization of Chemicals), and peer reviewed publications. Two additional species, Lemna gibba (macrophyte) and Ankistrodesmus falcatus (alga) were studied in exposures to dodecyl (C12) AO to provide sufficient taxonomic diversity to conduct a Species Sensitivity Distribution (SSD) analysis. The SSD 5th percentile hazardous concentration (HC5) to C12 AO was found to be 0.052mg/L which is similar to an existing AO 28-d, 3-community periphyton community bioassay normalized to C12 AO (No-observed-effect-concentration or NOEC=0.152mg/L). The statistical properties of the SSD was probed suggesting that new studies of additional taxa would be required that were at least 10-fold more sensitive than the most sensitive taxon to move the HC5 lower by a factor of 3. The overall AO hazard assessment suggests a large margin of safety relative to published environmental exposure data.

Widespread Microbial Adaptation to l-Glutamate-N,N-diacetate (L-GLDA) Following Its Market Introduction in a Consumer Cleaning Product.

l-Glutamate-N,N-diacetate (L-GLDA) was recently introduced in the United States (U.S.) market as a phosphate replacement in automatic dishwashing detergents (ADW). Prior to introduction, L-GLDA exhibited poor biodegradation in OECD 301B Ready Biodegradation Tests inoculated with sludge from U.S. wastewater treatment plants (WWTPs). However, OECD 303A Activated Sludge WWTP Simulation studies showed that with a lag period to allow for growth (40-50 days) and a solids retention time (SRT) that allows establishment of L-GLDA degraders (>15 days), significant biodegradation (>80% dissolved organic carbon removal) would occur. Corresponding to the ADW market launch, a study was undertaken to monitor changes in the ready biodegradability of L-GLDA using activated sludge samples from various U.S. WWTPs. Initially all sludge inocula showed limited biodegradation ability, but as market introduction progressed, both the rate and extent of degradation increased significantly. Within 22 months, L-GLDA was ready biodegradable using inocula from 12 WWTPs. In an OECD 303A study repeated 18 months post launch, significant and sustained carbon removal (>94%) was observed after a 29-day acclimation period. This study systematically documented field adaptation of a new consumer product chemical across a large geographic region and confirmed the ability of laboratory simulation studies to predict field adaptation.

An evaluation of the ability of chemical measurements to predict polycyclic aromatic hydrocarbon-contaminated sediment toxicity to Hyalella azteca.

The present study examined the ability of three chemical estimation methods to predict toxicity and nontoxicity of polycyclic aromatic hydrocarbon (PAH) -contaminated sediment to the freshwater benthic amphipod Hyalella azteca for 192 sediment samples from 12 field sites. The first method used bulk sediment concentrations of 34 PAH compounds (PAH34), and fraction of total organic carbon, coupled with equilibrium partitioning theory to predict pore-water concentrations (KOC method). The second method used bulk sediment PAH34 concentrations and the fraction of anthropogenic (black carbon) and natural organic carbon coupled with literature-based black carbon-water and organic carbon-water partition coefficients to estimate pore-water concentrations (KOCKBC method). The final method directly measured pore-water concentrations (pore-water method). The U.S. Environmental Protection Agency's hydrocarbon narcosis model was used to predict sediment toxicity for all three methods using the modeled or measured pore-water concentration as input. The KOC method was unable to predict nontoxicity (83% of nontoxic samples were predicted to be toxic). The KOCKBC method was not able to predict toxicity (57% of toxic samples were predicted to be nontoxic) and, therefore, was not protective of the environment. The pore-water method was able to predict toxicity (correctly predicted 100% of the toxic samples were toxic) and nontoxicity (correctly predicted 71% of the nontoxic samples were nontoxic). This analysis clearly shows that direct pore-water measurement is the most accurate chemical method currently available to estimate PAH-contaminated sediment toxicity to H. azteca.

Adsorption of polychlorinated biphenyls to activated carbon: equilibrium isotherms and a preliminary assessment of the effect of dissolved organic matter and biofilm loadings.

Sequestration of polychlorinated biphenyls (PCBs) by activated carbon (AC) has been proposed as a remediation strategy for PCB-contaminated sediments. However, published PCB-AC adsorption isotherm data are sparse and, while sediment-derived dissolved organic matter (DOM) and biofilms are likely to be present in sediments, the impacts of these loadings have not been quantified. Batch laboratory experiments were undertaken to obtain equilibrium adsorption capacities, q(e), for 9 PCBs on virgin AC, DOM-loaded AC, and biofilm-covered AC. Isotherm data fit the Freundlich isotherm equation (average R2=0.94, n=27) over the range of aqueous concentrations studied ( approximately 0.1-1000 ng/L). Planarity effects were evident at low aqueous concentrations only (0.1-10 ng/L), where q(e) of three PCBs of similar hydrophobicity decreased with an increasing number of ortho-chlorines, indicating steric hindrances attenuated adsorption. The values of q(e) for DOM- and biofilm-loaded ACs were approximately one order of magnitude smaller than those on virgin AC when normalized by the available AC surface area, indicating that PCB adsorption likely occurred on specific regions of the AC structure. Nevertheless, virgin and loaded ACs used in this study had sufficiently high PCB adsorption capacities to warrant further study as an in-situ remediation alternative for PCB-contaminated sediments.

Microcosm experiments to assess the effects of temperature and microbial activity on polychlorinated biphenyl transport in anaerobic sediment.

Increased polychlorinated biphenyl (PCB) loadings from sediment to the water column under low-flow conditions during late spring and summer months have been observed in the Grasse River (Massena, NY) and other PCB-contaminated rivers in the United States. Temperature appears to be an important factor affecting this phenomenon, as increased sediment temperature leads to increased microbial and bioturbator activity as well as increased rates of diffusion and desorption. Laboratory-scale sediment microcosms were developed and used to study with fine-scale resolution the effects of temperature and microbial activity on PCB transport in river sediment. Over the time course of these experiments, with the extraction procedures used, irreversible sorption of each congener to sediment was observed and increased with aging of the sediment. Temperature-dependent transport was observed for PCB congeners 2,4,5-trichlorobiphenyl (BZ29), 2,5-dichlorobiphenyl (BZ9), and 2-chlorobiphenyl (BZ1) in Grasse River sediment and a synthetic sediment system. The fastesttransport of the congeners occurred in biologically active Grasse River sediment followed by biologically inactive (autoclaved) Grasse River sediment, and synthetic sediment. The increased transport in biologically active sediment demonstrated the importance of microbial activity, in particular gas bubble generation, in PCB transport in near-surface sediments.

Long-term changes in quality of discharge water from abandoned underground coal mines in Uniontown Syncline, Fayette County, PA, USA.

Changes in water quality over 25 years have been documented for discharges from an extensive network of abandoned underground coal mines in the Uniontown Syncline, Fayette County, PA, USA. A baseline study of 136 mine discharges in the syncline was conducted in 1974-1975. In 1998-2000, follow-up water flow and quality monitoring was conducted at 21 selected discharges for 2 years to assess the degree of mine water-quality improvement since 1974-1975. The data from the two periods of time were compared, with consideration of differences in measurement methods. The degree and rate of water-quality improvement was found to be highly dependent on the amount and duration of flooding in the mine voids. Water quality of discharges from the substantially flooded mine voids improved significantly, going from acidic water with high sulfate and iron concentrations in 1974-1975 to alkaline water with substantially lower sulfate and iron concentrations in 1998-2000. In contrast, the water quality in the unflooded mines showed less improvement over the 25 years between studies. The water discharging from the unflooded mines in 1974-1975 was acidic with high sulfate concentrations and in 1998-2000 was still acidic but showed somewhat lower sulfate and iron concentrations, reflecting depletion of readily available pyrite. The data obtained provide insight into the potential and rate of natural amelioration of mine water quality in different abandoned underground coal mine systems.