The Influence of Extraction Procedure on Ion Concentrations in Sediment Pore Water

Sediment pore water has the potential to yield important information on sediment quality, but the influence of isolation procedures on the chemistry and toxicity are not completely known and consensus on methods used for the isolation from sediment has not been reached. To provide additional insight into the influence of collection procedures on pore water chemistry, anion (filtered only) and cation concentrations were measured in filtered and unfiltered pore water isolated from four sediments using three different procedures: dialysis, centrifugation, and vacuum. Peepers were constructed using 24-cell culture plates and cellulose membranes and vacuum extractors consisted of fused-glass air stones attached with airline tubing to 60-cc syringes. Centrifugation was accomplished at two speeds (2,500 and 10,000 g) for 30 min in a refrigerated centrifuge maintained at 4°C. Only minor differences in chemical characteristics and cation and anion concentrations were found among the different collecting methods with differences being sediment-specific. Filtering of the pore water did not appreciably reduce major cation concentrations, but trace metals (Cu and Pb) were markedly reduced. Although the extraction methods evaluated produced pore waters of similar chemistries, the vacuum extractor provided the following advantages over the other methods: ease of extraction, volumes of pore water isolated, minimal preparation time, and least time required for extraction of pore water from multiple samples at one time. Received: 24 July 1997/Accepted: 14 November 1997     

Comparison of methods for conducting marine and estuarine sediment porewater toxicity tests—extraction,storage, and handling techniques

A series of studies was conducted to compare different porewater extraction techniques and to evaluate the effects of sediment and porewater storage conditions on the toxicity of pore water, using assays with the sea urchin Arbacia punctulata. If care is taken in the selection of materials, several different porewater extraction techniques (pressurized squeezing, centrifugation, vacuum) yield samples with similar toxicity. Where the primary contaminants of concern are highly hydrophobic organic compounds, centrifugation is the method of choice for minimizing the loss of contaminants during the extraction procedure. No difference was found in the toxicity of pore water obtained with the Teflon® and polyvinyl chloride pressurized extraction devices. Different types of filters in the squeeze extraction devices apparently adsorbed soluble contaminants to varying degrees. The amount of fine suspended particulate material remaining in the pore water after the initial extraction varied among the methods. For most of the sediments tested, freezing and thawing did not affect the toxicity of porewater samples obtained by the pressurized squeeze extraction method. Pore water obtained by other methods (centrifugation, vacuum) and frozen without additional removal of suspended particulates by centrifugation may exhibit increased toxicity compared with the unfrozen sample.The toxicity of pore water extracted from refrigerated (4°C) sediments exhibited substantial short-term (days, weeks) changes. Similarly, sediment pore water extracted over time from a simulated amphipod solid-phase toxicity test changed substantially in toxicity. For the sediments tested, the direction and magnitude of change in toxicity of pore water extracted from both refrigerated and solid-phase test sediments was unpredictable.     

Toxicity Identification Evaluation of Lake Orta (Northern Italy) Sediments Using the Microtox System

Pore waters extracted by centrifugation from Lake Orta (Northern Italy) sediments were studied with a modified Toxicity Identification Evaluation (TIE) procedure using the Microtox bacterial luminescence toxicity test system. The most toxic pore water samples were from stations near a rayon factory, known as a source of copper and ammonium discharges. The TIE manipulations used were filtration, EDTA chelation, and C18 solid-phase resin adsorption. The most effective treatments to remove toxicity were the EDTA and C18, indicating that both metals and nonpolar organic compounds contribute to the observed toxicity.     

An in situ toxicity identification evaluation method Part II: Field validation

When sediments are found to be toxic usually there is a mixture of chemicals present. Often it is important to establish which chemicals contribute to the toxicity. Establishing causality can be difficult and often requires fractionation with subsequent toxicity testing. The sample collection and manipulation process can alter chemical bioavailability and toxicity. An in situ toxicity identification evaluation (iTIE) chamber is described that was placed in sediments and fractionated pore-water chemicals into nonpolar chemicals, metals, and ammonia-type groups. This method was field tested and compared to the laboratory-based, U.S. Environmental Protection Agency (U.S. EPA) toxicity identification evaluation (TIE) method. Field studies were performed at three sites contaminated primarily with polycyclic aromatic hydrocarbons (PAHs) (Little Scioto River, OH, USA), polychlorinated biphenyls (PCBs) (Dicks Creek, OH, USA), and chlorobenzenes (Sebasticook River, ME, USA). Both the iTIE and the U.S. EPA TIE methods used Daphnia magna in 24-h exposures. Although the iTIE and TIE were conducted on sediments from the same location, there was significantly more toxicity observed in the iTIE testing. The dominant chemical classes were separated by the iTIE method and revealed which fractions contributed to toxicity. The loss of toxicity in the TIE approach did not allow for subsequent fractionation and stressor identification. Advantages of the iTIE over the TIE method were greater sensitivity and ability to detect causative toxic chemical fractions; lack of sediment collection and subsequent manipulation; and, thus, reduction in potential artifacts, more realistic exposure with slow, continual pore-water renewal in situ, ability to evaluate pore waters in sandy or rocky substrates where pore waters are difficult to collect, and a quicker phase I evaluation. Limitations of the iTIE method as compared to the TIE methods were extensive pretest assembly process, fewer phase I fractionation possibilities, and restriction to shallow waters. The results of these studies suggest that the iTIE method provides a more accurate and sensitive evaluation of pore water toxicity than the laboratory TIE method.     

Causes of Sediment Toxicity to <Emphasis Type="Italic">Mytilus galloprovincialis</Emphasis> in San Francisco Bay,California

Since the San Francisco Regional Monitoring Program (RMP) sampling began, elutriate samples prepared with sediment from the Grizzly Bay monitoring station have been consistently toxic to bivalve larvae (Mytilus galloprovincialis). An investigation into the cause of toxicity was initiated with a Phase I Toxicity Identification Evaluation (TIE) using bivalve embryos. TIE results and chemical analyses of elutriate samples suggested that divalent metals were responsible for the observed toxicity. Following the initial characterization of trace metals as toxicants, additional TIEs were performed on elutriates prepared from three additional Grizzly Bay samples collected between 1997 and 2001. Additional TIEs included ethylenediamine tetraacetic acid (EDTA) treatments in a sediment-water interface (SWI) exposure system, and the use of a cation exchange column with serial elution of sample fractions with hydrochloric acid of increasing normality. EDTA significantly reduced toxicity in overlying water in the SWI system. The cation exchange column reduced both toxicity and concentrations of trace metals, and serial elution of the column added back both toxicity and specific metals contained in individual acid fractions. Chemical analyses of three elutriate samples demonstrated copper concentrations were within the range toxic to bivalves. Results of Phase I TIEs, additional Phase II treatments, SWI exposures, and metals analyses indicate the potential for metal toxicity in sediments from this estuarine site. When combined with the results of standard TIE methods, a solid-phase cation extraction and elution approach identified copper as the most probable cause of toxicity.     

Development of toxicity identification evaluation procedures for pyrethroid detection using esterase activity

Recent agrochemical usage patterns suggest that the use of organophosphate (OP) pesticides will decrease, resulting in a concomitant increase in pyrethroid usage. Pyrethroids are known for their potential toxicity to aquatic invertebrates and many fish species. Current toxicity identification evaluation (TIE) techniques are able to detect OPs, but have not been optimized for pyrethroids. Organophosphate identification methods depend upon the use of piperonyl butoxide (PBO) to identify OP-induced toxicity. However, the use of PBO in TIE assays will be confounded by the co-occurrence of OPs and pyrethroids in receiving waters. It is necessary, therefore, to develop new TIE procedures for pyrethroids. This study evaluated the use of a pyrethroid-specific antibody, PBO, and carboxylesterase activity to identify pyrethroid toxicity in aquatic toxicity testing with Ceriodaphnia dubia. The antibody caused significant mortality to the C. dubia. Piperonyl butoxide synergized pyrethroid-associated toxicity, but this effect may be difficult to interpret in the presence of OPs and pyrethroids. Carboxylesterase activity removed pyrethroid-associated toxicity in a dose-dependent manner and did not compromise OP toxicity, suggesting that carboxylesterase treatment will not interfere with TIE OP detection methods. These results indicate that the addition of carboxylesterase to TIE procedures can be used to detect pyrethroids in aquatic samples.     

Whole-sediment toxicity identification evaluation tools for pyrethroid insecticides: I. Piperonyl butoxide addition

Piperonyl butoxide (PBO) is a synergist used in some pyrethroid and pyrethrin pesticide products and has been used in toxicity identification evaluations (TIEs) of water samples to indicate organophosphate or pyrethroid-related toxicity. Methods were developed and validated for use of PBO as a TIE tool in whole-sediment testing to help establish if pyrethroids are the cause of toxicity observed in field-collected sediments. Pyrethroid toxicity was increased slightly more than twofold in 10-d sediment toxicity tests with Hyalella azteca exposed to 25 microg/L of PBO in the overlying water. This concentration was found to be effective for sediment TIE use, but it is well below that used in previous water and pore-water TIEs with PBO. The effect of PBO on the toxicity of several nonpyrethroids also was tested. Toxicity of the organophosphate chlorpyrifos was reduced by PBO, and the compound had no effect on toxicity of cadmium, DDT, or fluoranthene. Mixtures of the pyrethroid bifenthrin and chlorpyrifos were tested to determine the ability of PBO addition to identify pyrethroid toxicity when organophosphates were present in a sample. The PBO-induced increase in pyrethroid toxicity was not seen when chlorpyrifos was present at or above equitoxic concentrations with the pyrethroid. In the vast majority of field samples, however, the presence of chlorpyrifos does not interfere with use of PBO to identify pyrethroid toxicity. Eleven field sediments or soils containing pyrethroids and/or chlorpyrifos were used to validate the method. Characterization of the causative agent as determined by PBO addition was consistent with confirmation by chemical analysis and comparison to known toxicity thresholds in 10 of the 11 sediments.     

An in situ toxicity identification evaluation method Part I: Laboratory validation

Identification of individual chemical groups is critical in evaluating sediment quality and fractionating these groups of chemicals in a mixture is important to determine the primary chemicals causing toxicity. The in situ toxicity identification evaluation (iTIE) is a novel method that was developed to fractionate chemicals in contaminated sediments and waters and assess toxicity organisms. The study objectives were to verify that the iTIE can help identify contaminant chemical classes and improve the toxicity assessment process; and compare the iTIE and U.S. Environmental Protection Agency's (U.S. EPA) toxicity identification evaluation (TIE) methods. The iTIE exposure chamber is powered by a portable air pump that suctions pore water, via a Venturi system, through selective sorption materials. After passing through the sorptive materials, the pore water passes into an exposure chamber containing Daphnia magna. The chemical sorption materials included Ambersorb 563 for nonpolar organic chemical adsorption, Chelex for metals chelation, and multiple zeolite types for ammonia adsorption. The laboratory studies were performed using water and sediments spiked with ammonia, cadmium, and fluoranthene. The laboratory validation of the iTIE approach showed that different classes of compounds readily could be separated via the resin treatments, resulting in significant differences in concentrations and thus exposures to in situ exposed organisms. Ammonia, cadmium, and fluoranthene were significantly removed by zeolite, Chelex, and Ambersorb, respectively. Although there was some cross-adsorption to the other nontarget resins, it was limited and allowed for treatment differences to be detected. Survival in the treatment resins exposed to the target compounds was as high as control survivals. A 24-h exposure period appeared optimal, allowing for replacement of initial culture water with pore waters, while longer exposures occasionally allowed for breakthrough of contaminants. The iTIE was more sensitive than the U.S. EPA TIE method, in that it detected toxicity more readily due to the greater loss of contaminant concentrations in the TIE manipulation process.     

Sediment toxicity identification evaluation (TIE) studies at marine sites suspected of ordnance contamination

A sediment quality assessment survey and subsequent toxicity identification evaluation (TIE) study was conducted at several sites in Puget Sound, Washington. The sites were previously suspected of contamination with ordnance compounds. The initial survey employed sea urchin porewater toxicity tests to locate the most toxic stations. Sediments from the most toxic stations were selected for comprehensive chemical analyses. Based on the combined information from the toxicity and chemical data, three adjacent stations in Ostrich Bay were selected for the TIE study. The results of the phase I TIE suggested that organics and metals were primarily responsible for the observed toxicity in the sea urchin fertilization test. In addition to these contaminants, ammonia was also contributing to the toxicity for the sea urchin embryological development test. The phase II TIE study isolated the majority of the toxicity in the fraction containing nonpolar organics with high log K _ow, but chemical analyses failed to identify a compound present at a concentration high enough to be responsible for the observed toxicity. The data suggest that some organic or organometallic contaminant(s) that were not included in the comprehensive suite of chemical analyses caused the observed toxicological responses. Received: 12 December 2000/Accepted: 11 May 2001     

Development of a Toxicity Identification Evaluation Protocol Using Chlorophyll-<Emphasis Type="Italic">a</Emphasis> Fluorescence in a Marine Microalga

Growth inhibition bioassays with the microalga Nitzschia closterium have recently been applied in marine Toxicity Identification Evaluation (TIE) testing. However, the 48-h test duration can result in substantial loss of toxicants over time, which might lead to an underestimation of the sample toxicity. Although shorter-term microalgal bioassays can minimize such losses, there are few bioassays available and none are adapted for marine TIE testing. The acute (5-min) chlorophyll-a fluorescence bioassay is one alternative; however, this bioassay was developed for detecting herbicides in freshwater aquatic systems and its suitability for marine TIE testing was not known. In this study, a chlorophyll-a fluorescence bioassay using the marine microalga Isochrysis galbana was able to detect contaminants other than herbicides at environmentally relevant concentrations and tolerated the physical and chemical manipulations needed for a Phase I TIE. Phase I TIE procedures were successfully developed using this chlorophyll-a fluorescence bioassay and used to identify all classes of contaminants present in a synthetic mixture of known chemical composition. In addition, TIEs with both the acute fluorescence bioassay and the standard growth inhibition bioassay identified the same classes of toxicants in a sample of an unknown complex effluent. Even though the acute chlorophyll-a fluorescence end point was less sensitive than the chronic cell division end point, TIEs with the chlorophyll-a fluorescence bioassay provided a rapid and attractive alternative to longer-duration bioassays.     

Sequential toxicity identification evaluation (TIE) for characterizing toxicity of Venice Lagoon sediments: comparison of two different approaches

A toxicity identification evaluation phase-I (TIE-1) procedure was carried out on five pore water samples extracted from sediments of the Venice Lagoon previously investigated to assess both chemical contamination and toxic effects on the biota. Two different sequential TIE procedures were tested. A first sequence (TIE-1) provided for adding Na2S2O3, adding Na-EDTA, filtering, elution through a C18-SPE column and removing ammonia using the macroalgae Ulva rigida Agardh 1823, while a second procedure (TIE-2) was set up using U. rigida treatment for ammonia removal as first step, keeping unchanged the sequence of the other manipulations. Two different exposure time to the macroalgae were tested (3-h and 15-h). Sperm-cell toxicity test with the echinoid Paracentrotus lividus and embryotoxicity tests with the bivalves Mytilus galloprovincialis and Crassostrea gigas were performed on pore-water samples to assess the effect of the sequential treatments on the overall toxicity. The results confirmed that ammonia contribution to toxicity is strong in most of the samples and that metals, specially Cu, are of concern at least in three sites. The TIE-2 procedure provided more reliable results for the samples characterized by high ammonia contribution to the overall toxicity, whereas the results of TIE-1 and TIE-2 were equivalent for the samples where ammonia contribution was not prevailing. Chemical analyses and test results showed that a 3-h U. rigida exposure is suitable to remove ammonia toxicity minimizing potential metal up-take.     

Use of carboxylesterase activity to remove pyrethroid-associated toxicity to Ceriodaphnia dubia and Hyalella azteca in toxicity identification evaluations

Increases in the use and application of pyrethroid insecticides have resulted in concern regarding potential effects on aquatic ecosystems. Methods for the detection of pyrethroids in receiving waters are required to monitor environmental levels of these insecticides. One method employed for the identification of causes of toxicity in aquatic samples is the toxicity identification evaluation (TIE); however, current TIE protocols do not include specific methods for pyrethroid detection. Recent work identified carboxylesterase treatment as a useful method for removing/detecting pyrethroid-associated toxicity. The present study has extended this earlier work and examined the ability of carboxylesterase activity to remove permethrin- and bifenthrin-associated toxicity to Ceriodaphnia dubia and Hyalella azteca in a variety of matrices, including laboratory water, Sacramento River (CA, USA) water, and Salinas River (CA, USA) interstitial water. Esterase activity successfully removed 1,000 ng/L of permethrin-associated toxicity and 600 ng/L of bifenthrin-associated toxicity to C. dubia in Sacramento River water. In interstitial water, 200 ng/L of permethrin-associated toxicity and 60 ng/L of bifenthrin-associated toxicity to H. azteca were removed. The selectivity of the method was validated using heat-inactivated enzyme and bovine serum albumin, demonstrating that catalytically active esterase is required. Further studies showed that the enzyme is not significantly inhibited by metals. Matrix effects on esterase activity were examined with municipal effluent and seawater in addition to the matrices discussed above. Results confirmed that the esterase retains catalytic function in a diverse array of matrices, suggesting that this technique can be adapted to a variety of aquatic samples. These data demonstrate the utility of carboxylesterase treatment as a viable step to detect the presence of pyrethroids in receiving waters.     

Horizon-specific oxidation of acid volatile sulfide in relation to the toxicity of cadmium spiked into a freshwater sediment

The effects of oxidative processes on acid volatile sulfide (AVS) concentrations in various horizons of whole sediment cores were evaluated in relation to the toxicity of a metal (cadmium). An artificial system was used to age cadmium-spiked sediment samples under a constant flow of fresh Lake Superior water. Sediments from Pequaywan Lake, Minnesota (12 mol AVS/g) were spiked to achieve (nominal) cadmium: AVS molar ratios of 0.02 (control), 0.2, 0.8, 1.2, and 3.0. At 0, 24, and 48 days post-spiking, sediment cores were removed from the aging system and tested for toxicity to the amphipod Hyalella azteca. At the same time, horizons from replicate sediment cores were prepared for analysis by freezing, and then cutting them into 10–20 mm increments. The sediment horizons were analyzed for AVS and simultaneously extracted cadmium concentrations, and pore water concentrations of cadmium. Relatively little oxidation of surficial AVS concentrations was observed, even at aging times up to 48 d. By 48 d, pore water concentrations of cadmium were slightly elevated at all spiking concentrations, but were increased greatly at cadmium:AVS ratios greater than one. Hyalella azteca mortality was generally predictable based on surficial cadmium:AVS ratios or pore water cadmium concentrations.     

An assessment of in vitro androgenic activity and the identification of environmental androgens in United Kingdom estuaries

Environmental androgens are a group of compounds that to date have received very little attention. In this study, a yeast-based androgen screen (YAS) was used to determine the level of in vitro androgenic activity in seven United Kingdom estuaries. Surface water, sediment pore water, and sediment particulate material solvent extracts collected from Southampton Water, the Thames, Mersey, Tees, Tyne, Clyde, and Forth were tested for in vitro androgenic activity. Eleven of the 41 surface water samples collected displayed androgenic activity >2 ng dihydrotestosterone (DHT) equivalents/L (3-9 ng DHT/L), while eight of the 39 sediment pore waters collected showed activity >45 ng DHT/L (51-187 ng DHT/L). High levels of androgenic activity were determined in the solvent extracts of sediments, with 10 of 39 samples exhibiting a level of androgenic activity >454 ng DHT/kg (1,020-15,300 ng DHT/kg). In vitro YAS testing of five selected sewage treatment works (STW) effluents entering these estuaries showed that measurable levels (34-635 ng DHT/L) of androgenic activity were observed in those receiving only primary treatment (Howdon STW and Irvine Valley Sewer) at the time of the survey. A toxicity identification evaluation (TIE) study of Irvine Valley Sewer effluent using the YAS assay was used to identify the natural steroids/steroid metabolites dehydrotestosterone, androstenedione, androstanedione, 5beta-androstane-3alpha,11beta-diol-17-one, androsterone, and epi-androsterone as responsible for 99% of the in vitro activity determined in the effluent.     

Toxicity Identification Evaluation of Five Metals Performed with Two Organisms (Daphnia magna and Lactuca sativa)

When trying to identify the main toxicants in effluents, natural waters, sediments, soil leachates, and leachates from products, the Toxicity Identification Evaluation (TIE) procedure has proven useful. To enhance the use of this procedure for soil, sewage, and sediment samples, we wanted to evaluate this TIE procedure, regarding metal toxicity, for the 96-h root elongation test performed with Lactuca sativa (lettuce) seeds. We also wanted to evaluate the effect of TIE treatment on the toxicity of Mn and Fe to Daphnia magna. Bioassays were performed with Daphnia magna (48-h immobility) and lettuce seeds (96-h root elongation) to determine the effect concentrations for both organisms of Ag, Cu, Fe, Mn, and Zn. The TIE was then performed at the determined Daphnia 48-h EC₈₄ and Lactuca 96-h EC₅₀ for each metal. Our results showed that the order of the metal toxicity was Ag>Cu>Zn>Fe>Mn, for Daphnia and Ag = Zn = Fe = Cu > Mn for lettuce seeds. We also found that toxicity of the metals for Daphnia magna was reduced according to the prevailing knowledge regarding Cu, Zn, and Ag. However, the toxicity of Ag and Cu for Daphnia was also reduced by filtration through a C18 resin. Toxicity of Mn and Fe was reduced by filtration through a CM resin and increase of pH. For lettuce seeds, toxicity of the metals was reduced by the same treatments as for Daphnia magna with the exception of EDTA addition, which did not affect Cu toxicity to lettuce seeds. No effects were found for filtration through a C18 resin. We suggest that the TIE procedure using lettuce seeds can be used in toxicity identification of metals. However, the effects of pH manipulations were often stronger with lettuce and should be interpreted with care.     

Toxicity of Sediment Collected Upriver and Downriver of Major Cities Along the Lower Mississippi River

The Lower Mississippi River contributes significantly to the biodiversity and ecological stability of the alluvial valley, but agricultural, industrial, and municipal developments have historically impacted environmental quality of the river. Toxicity of sediment and sediment pore water was used to assess the current effects of major cities on sediment quality along the Lower Mississippi River. Composite sediment samples were collected from four sites upriver and four sites downriver of five major cities: Cairo, IL; Memphis, TN; Vicksburg, MS; Baton Rouge, LA; and New Orleans, LA. Acute toxicity was determined by exposing Hyalella azteca to solid-phase sediment for 10 days with two water renewals per day and to sediment pore water under static conditions for 96 h. After the initial tests, animals were exposed to ultraviolet light for 16 h. Sediments were analyzed for organics (organochlorine pesticides, PCBs, organophosphate insecticides, and PAHs) and metals (Cr, Cu, Pb, Mn, Ni, Zn). With the exception of upriver from Memphis, solid-phase sediments were not toxic to H. azteca. Pore water from sediments collected upriver of Memphis also showed slight toxicity. Exposure of H. azteca to ultraviolet light did not increase the toxicity of the sediment or pore-water samples, indicating a lack of toxicity from PAHs that are photoactivated by ultraviolet light. Chemical analyses did not reveal any contaminant levels of concern in the sediments. Based on toxicity testing and chemical analyses, quality of sediments collected from the Lower Mississippi was good, with the exception of sites sampled upriver of Memphis. Received: 3 June 1997/Accepted: 22 December 1997     

Whole sediment toxicity identification evaluation tools for pyrethroid insecticides: III. Temperature manipulation

Since the toxicity of pyrethroid insecticides is known to increase at low temperatures, the use of temperature manipulation was explored as a whole-sediment toxicity identification evaluation (TIE) tool to help identify sediment samples in which pyrethroid insecticides are responsible for observed toxicity. The amphipod Hyalella azteca is commonly used for toxicity testing of sediments at a 23 degrees C test temperature. However, a temperature reduction to 18 degrees C doubled the toxicity of pyrethroids, and a further reduction to 13 degrees C tripled their toxicity. A similar response, though less dramatic, was found for 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (DDT), and dissimilar temperature responses were seen for cadmium and the insecticide chlorpyrifos. Tests with field-collected sediments containing pyrethroids and/or chlorpyrifos showed the expected thermal dependency in nearly all instances. The inverse relationship between temperature and toxicity provides a simple approach to help establish when pyrethroids are the principal toxicant in a sediment sample that could be used as a supplemental tool in concert with chemical analysis or other TIE manipulations. The phenomenon appears to be, in part, a consequence of a reduced ability to biotransform the toxic parent compound at cooler temperatures. The strong dependence of pyrethroid toxicity on temperature has important ramifications for predicting their environmental effects, and the standard test temperature of 23 degrees C dramatically underestimates risk to resident fauna during the cooler months.     

Evidence of pesticide impacts in the Santa Maria River watershed, California, USA

The Santa Maria River provides significant freshwater and coastal habitat in a semiarid region of central California, USA. We conducted a water and sediment quality assessment consisting of chemical analyses, toxicity tests, toxicity identification evaluations, and macroinvertebrate bioassessments of samples from six stations collected during four surveys conducted between July 2002 and May 2003. Santa Maria River water samples collected downstream of Orcutt Creek (Santa Maria, Santa Barbara County, CA, USA), which conveys agriculture drain water, were acutely toxic to cladocera (Ceriodaphnia dubia), as were samples from Orcutt Creek. Toxicity identification evaluations (TIEs) suggested that toxicity to C. dubia in Orcutt Creek and the Santa Maria River was due to chlorpyrifos. Sediments from these two stations also were acutely toxic to the amphipod Hyalella azteca, a resident invertebrate. The TIEs conducted on sediment suggested that toxicity to amphipods, in part, was due to organophosphate pesticides. Concentrations of chlorpyrifos in pore water sometimes exceeded the 10-d median lethal concentration for H. azteca. Additional TIE and chemical evidence suggested sediment toxicity also partly could be due to pyrethroid pesticides. Relative to an upstream reference station, macroinvertebrate community structure was impacted in Orcutt Creek and in the Santa Maria River downstream of the Creek input. This study suggests that pesticide pollution likely is the cause of ecological damage in the Santa Maria River.     

Establishing cause-effect relationships in hydrocarbon-contaminated sediments using a sublethal response of the benthic marine alga, Entomoneis cf punctulata

A sublethal whole-sediment toxicity test that uses flow cytometry to measure inhibition of esterase activity in the marine microalga Entomoneis cf punctulata was applied to the assessment of hydrocarbon-contaminated sediments and toxicity identification and evaluation (TIE). Concentration-response relationships were developed, and a 20% effect concentration for total polycyclic aromatic hydrocarbons (PAHs) of 60 mg/kg normalized to 1% total organic carbon was calculated. Relationships between toxic effects and sediment organic carbon concentrations, organic carbon forms (e.g., black carbon), and sediment particle size indicated that further normalization of hydrocarbon concentrations to sediment particle size may improve concentration-response relationships. The algal toxicity test was applied as a rapid whole-sediment TIE procedure that involved the addition to sediment of powdered coconut charcoal (PCC), a hydrophobic, carbon-based material that strongly adsorbs PAHs and decreases the pore-water exposure pathway. Sediments with PCC concentrations of up to 15% (w/w) provided acceptable responses in control sediments. For six sediments with total PAH concentrations of 1,060, 4,060, 5,120, 9,150, 9,900, and 15,900 mg/kg, inhibition of E. cf punctulata esterase activity (% of control) was 75, 97, 94, 93, 100, and 97%, respectively. Following a 15% PCC amendment to these sediments, inhibition of esterase activity was 0, 1, 11, 69, 32, and 68%, respectively, indicating a decrease in toxicity in all sediments. Because the alga E. cf punctulata is exposed to toxicants via both pore water and overlying water, the reduction in toxicity achieved by 15% PCC additions can be related to the efficient removal of dissolved hydrocarbons released from sediment particles. The sediment-PCC manipulations coupled with algal whole-sediment toxicity tests provided an effective and rapid TIE method to determine whether hydrocarbon contaminants are responsible for toxicity in sediments.     

Marine sediment toxicity identification evaluation methods for the anionic metals arsenic and chromium

Marine sediments accumulate a variety of contaminants and, in some cases, demonstrate toxicity because of this contamination. Toxicity identification evaluation (TIE) methods provide tools for identifying the toxic chemicals causing sediment toxicity. Currently, whole-sediment TIE methods are not available for anionic metals like arsenic and chromium. In the present paper, we describe two new anion-exchange resins used in the development of whole-sediment TIE methods for arsenic and chromium. Resins were shown to reduce whole-sediment toxicity and overlying water concentrations of the anionic metals. Sediment toxicity, expressed as the median lethal concentration, was reduced by a factor of two to a factor of nearly six between amended sediment treatments containing resin and those without resin. Aqueous concentrations of arsenic and chromium in the toxicity exposures decreased to less than the detection limits or to concentrations much lower than those measured in treatments without resin. Interference studies indicated that the anion-exchange resins had no significant effect on concentrations of the representative pesticide endosulfan and minimal effects on concentrations of ammonia. However, the anion-exchange resins did significantly reduce the concentrations of a selection of cationic metals (Cd, Cu, Ni, Pb, and Zn). These data demonstrate the utility of anion-exchange resins for determining the contribution of arsenic and chromium to whole-sediment toxicity. The present results also indicate the importance of using TIE methods in a formal TIE structure to ensure that results are not misinterpreted. These methods should be useful in the performance of marine whole-sediment TIEs.