Observed and modeled seasonal trends in dissolved and particulate Cu, Fe, Mn, and Zn in a mining-impacted stream.

North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with discharge directly related to snowmelt and strong seasonal storms. Additionally, conditions in the stream cause rapid precipitation of large amounts of hydrous iron oxides (HFO) that sequester metals. Because AMD-impacted systems are complex, geochemical modeling may assist with predictions and/or confirmations of processes occurring in these environments. This research used Visual-MINTEQ to determine if field data collected over a two and one-half year study would be well represented by modeling with a currently existing model, while limiting the number of processes modeled and without modifications to the existing model's parameters. Observed distributions between dissolved and particulate phases in the water column varied greatly among the metals, with average dissolved fractions being >90% for Mn, approximately 75% for Zn, approximately 30% for Cu, and <10% for Fe. A strong seasonal trend was observed for the metals predominantly in the dissolved phase (Mn and Zn), with increasing concentrations during base-flow conditions and decreasing concentrations during spring-runoff. This trend was less obvious for Cu and Fe. Within hydrologic seasons, storm events significantly influenced in-stream metals concentrations. The most simplified modeling, using solely sorption to HFO, gave predicted percentage particulate Cu results for most samples to within a factor of two of the measured values, but modeling data were biased toward over-prediction. About one-half of the percentage particulate Zn data comparisons fell within a factor of two, with the remaining data being under-predicted. Slightly more complex modeling, which included dissolved organic carbon (DOC) as a solution phase ligand, significantly reduced the positive bias between observed and predicted percentage particulate Cu, while inclusion of hydrous manganese oxide (HMO) yielded model results more representative of the observed percentage particulate Zn. These results indicate that there is validity in the use of an existing model, without alteration and with typically collected water chemistry data, to describe complex natural systems, but that processes considered optimal for one metal might not be applicable for all metals in a given water sample.

Differential resistance to copper and mine drainage in Daphnia longispina: relationship with allozyme genotypes.

Differential resistance to metal pollution in Daphnia longispina populations was reported in previous studies. In this work, we tried to determine if variation in polymorphic enzymes, often referred as being under metal selection, were related with differences in resistance to acute single- and mixed-metal exposure. Allozyme genotype of 20 putatively polymorphic enzymes, 48-h median lethal concentration (LC50) for copper, and median lethal time (LT50) for a 3% dilution of acid mine drainage (AMD) were determined for 24 lineages of D. longispina. The copper LC50s ranged from 29.3 to 226 microg/L, and the AMD LT50s ranged from 48 min to 25 h and 29 min, with a strong correlation between both end points. Five distinct multilocus genotypes were identified based on polymorphisms in glucose-6-phosphate isomerase, lactate dehydrogenase, malate dehydrogenase, nicotinamide adenine dinucleotide phosphate (NADP+), phosphoglucomutase, and peroxidase. No differences were found in average genotype sensitivity for both toxicity end points or in genotype frequencies between the resistant- and sensitive-lineage groups. The results obtained indicate that allozyme genotype is not associated with increased resistance to acute metal stress in D. longispina.

Protective effects of allozyme genotype during chemical exposure in the grass shrimp, Palaemonetes pugio.

The primary objective of this research was to determine if the genotype of the enzymes glucose phosphate isomerase (Gpi), phosphoglucomutase (Pgm), or mannose phosphate isomerase (Mpi) are factors affecting survival during acute endosulfan, fluoranthene, and chromium(VI) exposures. Palaemonetes pugio were exposed in the laboratory to 6.3 microg/L endosulfan, 100 mg/L chromium(VI), or 0.6 mg/L fluoranthene. Dead shrimp were removed at approximately 15-30 min intervals and the individual's genotypes for the Gpi, Mpi, and Pgm enzymes were determined. These data were used to establish whether allozyme genotype was related to tolerance as analyzed with non-parametric methods (i.e. development of survival curves using the Kaplan-Meier method of estimation) and parametric methods (i.e. proportional hazards models). Since the sex and/or size of the organism was expected to affect tolerance, these variables were accounted for in the proportional hazards models. Results indicated individuals that were heterozygous (MF) for the Gpi allozyme survived longer and had less overall mortality than the homozygous MM genotype when exposed to chromium(VI) and to fluoranthene. No allozyme genotypes were related to tolerance during the endosulfan exposure when sex was included as a covariate in the analysis. These results support the hypothesis that there is a genetic basis for tolerance in P. pugio during acute exposures to chromium(VI) and to fluoranthene. Although a relationship between Gpi genotype and contaminant tolerance has been identified in previous studies, no such relationship has been documented in P. pugio or with chromium(VI) as the contaminant.

Spatial variations in the fate and transport of metals in a mining-influenced stream, North Fork Clear Creek, Colorado.

North Fork Clear Creek (NFCC) receives acid-mine drainage (AMD) from multiple abandoned mines in the Clear Creek Watershed. Point sources of AMD originate in the Black Hawk/Central City region of the stream. Water chemistry also is influenced by several non-point sources of AMD, and a wastewater treatment plant (WWTP). In-stream conditions immediately downstream from point-source inputs result in a visual and rapid precipitation of hydrous iron oxides (HFO). Hydrous manganese oxides (HMO) are seen to coat rocks further downstream during some seasons. Synoptic spatial sampling was used to assess the fate and transport of Cu, Fe, Mn, and Zn during different years and hydrological seasons. Visual-MINTEQ was used to compare observed and model-calculated percentage particulate Cu and Zn as influenced by sorption to both HFO and HMO and aqueous complexation with dissolved organic carbon (DOC). Over distance, Cu and Fe were transported predominantly in the particulate phase, Mn in the dissolved phase, and Zn was intermediate in its distribution, with generally about 50% being in each phase. Under higher flows, a larger fraction of the total metals was present in the dissolved phase, along with a lower total suspended sediment (TSS) concentration. This is consistent with the source of TSS being predominantly in-stream precipitation of metals, which might be kinetically limited under higher flows. Modeling results most closely represented observed percentage particulate Cu under lower flows; a strong seasonal trend was not evident for Zn. Model over-predictions of percentage particulate Cu suggest non-equilibrium with sorbent phases or that something in addition to DOC was keeping a portion of the Cu in solution; under-predictions for Zn suggest an additional sorbent. Differences between observed and modeled particulate varied significantly between sites and seasons; ranging from 1 to 54% for Cu and 1 to 34% for Zn overall.