Use of zeolite for removing ammonia and ammonia-caused toxicity in marine toxicity identification evaluations.

Ammonia occurs in marine waters including effluents, receiving waters, and sediment interstitial waters. At sufficiently high concentrations, ammonia can be toxic to aquatic species. Toxicity identification evaluation (TIE) methods provide researchers with tools for identifying aquatic toxicants. For identifying ammonia toxicity, there are several possible methods including pH alteration and volatilization, Ulva lactuca addition, microbial degradation, and zeolite addition. Zeolite addition has been used successfully in freshwater systems to decrease ammonia concentrations and toxicity for several decades. However, zeolite in marine systems has been used less because ions in the seawater interfere with zeolite's ability to adsorb ammonia. The objective of this study was to develop a zeolite method for removing ammonia from marine waters. To accomplish this objective, we performed a series of zeolite slurry and column chromatography studies to determine uptake rate and capacity and to evaluate the effects of salinity and pH on ammonia removal. We also assessed the interaction of zeolite with several toxic metals. Success of the methods was also evaluated by measuring toxicity to two marine species: the mysid Americamysis bahia and the amphipod Ampelisca abdita. Column chromatography proved to be effective at removing a wide range of ammonia concentrations under several experimental conditions. Conversely, the slurry method was inconsistent and variable in its overall performance in removing ammonia and cannot be recommended. The metals copper, lead, and zinc were removed by zeolite in both the slurry and column treatments. The zeolite column was successful in removing ammonia toxicity for both the mysid and the amphipod, whereas the slurry was less effective. This study demonstrated that zeolite column chromatography is a useful tool for conducting marine water TIEs to decrease ammonia concentrations and characterize toxicity.

Precision of dialysis (peeper) sampling of cadmium in marine sediment interstitial water.

Isolating and analyzing interstitial water (IW) during sediment toxicity tests enables researchers to relate concentrations of contaminants to responses of organisms, particularly when IW is a primary route of exposure to bioavailable contaminants by benthic dwelling organisms. We evaluate here the precision of sampling IW with the dialysis or 'peeper' method using sediments spiked with five different concentrations of cadmium. This method is one of several that are commonly used for collecting IW. Seven consecutive ten-day toxicity tests were conducted on these sediments and IW samples were collected at the end of each of these tests. Prior to each test initiation and insertion of IW samplers, sediments were allowed to equilibrate for seven days under flow-through conditions with filtered seawater. At the end of each ten-day testing period, peepers were retrieved, and IW cadmium measured. Data sets were organized by treatment and test number. Coefficients of variation (CV) for the six replicates for each sediment and testing period and for each sediment across testing periods (42 replicates) was used as a measure of sampling precision. CVs ranged from 25 to 206% when individual testing periods were considered, but ranged from 39 to 104% when concentrations for all testing periods were combined. However, after removal of outliers using Dixon's Criteria, the CVs improved and ranged from 6 to 88%. These levels of variability are comparable to those reported by others. The variability shown is partially explained by artifacts associated with the dialysis procedure, primarily sample contamination. Further experiments were conducted that support our hypothesis that contamination of the peeper causes much of the variability observed. If method artifacts, especially contamination, are avoided the dialysis procedure can be a more effective means for sampling IW metal.

Removal of ammonia toxicity in marine sediment TIEs: a comparison of Ulva lactuca, zeolite and aeration methods.

Toxicity Identification Evaluations (TIEs) can be used to determine the specific toxicant(s), including ammonia, causing toxicity observed in marine sediments. Two primary TIE manipulations are available for characterizing and identifying ammonia in marine sediments: Ulva lactuca addition and zeolite addition. In this study, we compared the efficacy of these methods to (1) remove NH(x) and NH(3) from overlying and interstitial waters and (2) reduce toxicity to the amphipod Ampelisca abdita and mysid Americamysis bahia using both spiked and environmentally contaminated sediments. The utility of aeration for removing NH(x) and NH(3) during a marine sediment TIE was also evaluated preliminarily. In general, the U. lactuca and zeolite addition methods performed similarly well at removing spiked NH(x) and NH(3) from overlying and interstitial waters compared to an unmanipulated sediment. Toxicity to the amphipod was reduced approximately the same by both methods. However, toxicity to the mysid was most effectively reduced by the U. lactuca addition indicating this method functions best with epibenthic species exposed to ammonia in the water column. Aeration removed NH(x) and NH(3) from seawater when the pH was adjusted to 10; however, very little ammonia was removed at ambient pHs ( approximately 8.0). This comparison demonstrates both U. lactuca and zeolite addition methods are effective TIE tools for reducing the concentrations and toxicity of ammonia in whole sediment toxicity tests.

Metal-colloid partitioning in artificial interstitial waters of marine sediments: influences of salinity, pH, and colloidal organic carbon concentration.

For decades, heavy metals have been deposited into marine sediments as a result of anthropogenic activities. Depending on their bioavailability, these metals may represent a risk to benthic organisms. Dissolved interstitial water metal concentrations have been shown to be better predictors of bioavailability than sediment metal concentrations. In order to improve our understanding of metals bioavailability in sediments, it is essential to fully comprehend metal speciation. Colloidal organic carbon is ubiquitous in marine interstitial water and readily forms complexes with numerous dissolved metals, greatly reducing their bioavailability. Methods were applied to isolate dissolved and colloidal cadmium, copper, nickel, lead, and zinc from interstitial waters using centrifugation and stirred cell ultrafiltration. Influences of salinity, pH, and colloidal carbon concentration on partitioning behavior were investigated. In the pH study, colloidal-dissolved partitioning of each metal (Kp) was observed to increase as pH rose. Conversely, in the salinity experiment, metal Kps declined as salinity increased. For the metal-organic colloid study, linear isotherms were calculated for each of the metals, resulting in log Kcocs ranging from 5.90 for zinc to 7.50 for copper. Kp values calculated from metal-spiked field sediments were in good agreement with those measured in the salinity study. These results provide insight into the behavior of metals associated with colloidal organic carbon in marine sediments under the conditions occurring in estuarine systems.

Exploratory analysis of the effects of particulate characteristics on the variation in partitioning of nonpolar organic contaminants to marine sediments.

The partitioning of nonpolar organic contaminants to marine sediments is considered to be controlled by the amount of organic carbon present. However, several studies propose that other characteristics of sediments may affect the partitioning of contaminants. For this exploratory analysis, we measured 19 sediment characteristics from five marine sediments and 11 characteristics of humic acids extracted from the sediments. These characteristics included elemental composition, grain size, soot carbon, polarity indices and molar ratios. Each individual characteristic and combinations of these characteristics were then used to normalize partition coefficients (Kp) generated for three organic contaminants: lindane, fluoranthene and a tetrachlorinated biphenyl (PCB). A coefficient of variation (CV) was then calculated for each contaminant to determine which normalization characteristic (individually or in combination) resulted in the lowest variability in partitioning between study sediments. For lindane and the PCB. normalization by the amount of sediment organic carbon resulted in the lowest variability in partition coefficients with CVs of 16.2% and 37.7%. respectively. However, normalization of fluoranthene by silt content resulted in lower CVs than those generated by organic carbon normalization: 31.0% vs. 37.6%. Normalization of contaminants Kp's by combined values of sediment characteristics resulted in lower CVs but only by a few percent. Using humic acid characteristics, humic organic carbon reduced variability between sediments most effectively. But only the normalized fluoranthene values had a CV (i.e., 25.4%) lower than the one based on normalization by sediment characteristics. When combined, humic acid characteristics resulted in lower CVs than normalization by individual or combinations of sediment characteristics for fluoranthene and the PCB with CVs of 19.3% and 28.7%, respectively. This analysis indicates variability associated with the partitioning of some organic contaminants to marine sediments can be further reduced when normalization by sediment characteristics other than organic carbon are utilized.