1、 - _ . STD.API/PETRO PUBL iibbb-ENGL 1999 5 O732290 ObLbLi-1 Li7T I American Petroleum Institute L- THE TOXICITY OF COMMON IONS TO FRESHWATER AND MARINE ORGANISMS Na HEALTH AND ENVIRONMENTAL SCIENCES DEPARTMENT PUBLICATION NUMBER 4666 F- ApRn. 1999 HCO, Mg+ CI SO:- Bir (Less Toxic) (More Toxic) F B,
2、O:- K HCO, Ca2 Mg Bi- SO:- (Less Toxic) To freshwater organisms, Mg, HCO;, and K were the most toxic, generally causing acute toxicity at less than 1,000 mg/L. While Br was one of the least acutely toxic ions to freshwater organisms, it had apparent chronic effects at much lower concentrations. To m
3、arine test organisms, HCO;, K, B40:-, and F- caused acute toxicity at lower concentrations than the other ions evaluated; Si.2 may also cause toxicity to Menidia berylha at approximately 200 mg/L. As with many toxicants, the complexity of common ion toxicity is associated with the chemistry of efflu
4、ents and the interactions of all the chemicals within that effluent. This relationship is especially true in waters of high ionic strength such as those discharged to marine environments. Because some ions may be near saturation and can form strong bonds with other materials, toxicity may be reduced
5、 through complexation and precipitation of salts. Toxicity, therefore, cannot always be defined in terms of the concentration of one or more ions, as measured in an analytical laboratory; rather, the chemistry of the whole effluent, including such modifying factors as temperature, atmospheric pressu
6、re, carbon dioxide concentration, and pH may be considered. Isolation of the causative toxicant(s) in an effluent may require investigations along several lines in a toxicity identification evaluation. In addition to comparing measured ion concentrations with historic literature, the use of syntheti
7、c or “mock” effluents and computer models can prove useful. Even these multiple lines of evidence may prove inconclusive in some cases where toxicity is associated with common ions and other organic or inorganic compounds. STD.API/PETRO PUBL 4666-ENGL 3979 9 0732290 O636333 193 P PHYSIOLOGICAL ROLE
8、OF COMMON IONS Several of the ions reviewed in this report are essential to aquatic organisms in various metabolic activities, as well as to maintain a favorable intra- and extracellular environment in which those activities occur. Calcium, for example, in addition to being critical in building skel
9、etal structures, also contributes significantly to the regulation of membrane permeability and control of the gating of Na+-fluxes in the nerve membrane, and is also an essential cofactor in blood clotting and for digestion. Because of the importance of Ca2 and other ions to physiological processes,
10、 organisms have developed mechanisms for maintaining intra- and extracellular ion concentrations within the favorable ranges that individual species can tolerate. Mechanisms include active excretion or absorption of ions through gills or other structures and adjustments in the permeability of cellul
11、ar tight junctions. CONCLUSIONS Common ions have been found to cause toxicity in effluents from several different sources, including gas and oil production, chemical manufacturing, refining, agriculture, and seawater desalination. In a large number of studies, the concentrations of ions that are lik
12、ely to cause adverse effects on aquatic organisms have been identified. While most of these studies have addressed acute toxicity, chronic effects have also been investigated and may become increasingly important as the inclusion of short-term chronic studies becomes more commonplace in NPDES permit
13、s. Organisms that are commonly used in NPDES WET tests differ in their responses to these ions, with some, such as Cyprinocfon variegatus, being much more tolerant to low and high ion concentrations than others. While in many cases toxicity can be associated with specific ions, adverse effects often
14、 are difficult to quantify, particularly in high ionic strength solutions, due to the interactions that common ions have with each other and with other organic and inorganic constituents. The identification of ion toxicity, therefore, often involves using not only historical toxicity data but also t
15、raditional TIE methods and computer modeling to provide a weight of evidence approach to toxicity identification. Because many of these ions are essential nutrients to aquatic organisms and may normally be present in source and receiving water, it may be appropriate to evaluate the potential impacts
16、 of ion toxicity, as found in laboratory studies, in light of the ecology of the receiving environment. ES-3 Section I INTRODUCTION It has long been recognized that some chemical constituents, when present in the aquatic environment above certain levels, may be toxic to organisms. Aquatic toxicology
17、 can, in fact, be defined as “the qualitative and quantitative study of the adverse or toxic effects of chemicals and other anthropogenic materials or xenobiotics on aquatic organisms“ (Rand and Petrocelli, 1985). Typically, any reference to “toxic materials“ usually is associated with complex synth
18、etic chemicals or heavy metals. However, common constituents found in aquatic environments can also be toxic to aquatic organisms when present in sufficient quantities. Ions such as potassium, magnesium, and calcium are present naturally in water and are part of a group of elements that are essentia
19、l to proper organism function. When concentrations of these common ions exceed a certain level or, in the case of some essential ions, are below a certain level, adverse effects can occur. The issue of ion imbalance in effluents recently has been highlighted in a re-evaluation of EPAs whole effluent
20、 toxicity (WET) testing program. Waters with substantially elevated salinity or total dissolved solids (TDS) have been shown to be toxic when ionic constituents are not in the same proportions as in natural saline waters. High-TDS effluents from operations utilizing water conservation have also show
21、n toxicity. Many processes in manufacturing plants result in a high-TDS effluent with disproportionate ionic ratios. Examples of effluent that may have ion imbalances include those from oil and gas production, water conservation or recycled process waters, and caustic/basic treatment processes using
22、 CaCO, neutralization. The process of increasing effluent salinity (“salting-up“) to accommodate marine/estuarine organism tolerances also can result in toxicity. SCOPE OF REVIEW This review focuses on laboratory data regarding the effects of common cations and anions on both freshwater and marine o
23、rganisms. While a given water can have a variety of constituents, only a few are considered to be common. The major cations are calcium (Ca +), magnesium (Mg“), potassium (K+), sodium (Na), and strontium (Sr*+), and the major anions are bicarbonate (HCO;), borate (B,07 -), bromide (Br), chloride (CI
24、-), fluoride (F-), and sulfate (SO:-). This document provides a general summary of the results of toxicity studies on ions and explores the physiological effects of those ions on a tissue and cellular basis. 1-1 Section 1 describes some of the current regulatory schemes concerned about ion toxicity.
25、 Section 2 summarizes the ionic composition of natural waters in the world, both fresh and saline. A review of some of the sources of high TDS waters is provided in Section 3, along with a discussion of Toxicity Identification Methods (TIE) and what techniques are effective in separating toxicity re
26、lated to common ions from toxicity due to other constituents. Section 4 is a review of the toxicological data for different ions. Section 5 explores the physiological function of ions and the various models of ion regulation that exist in different taxa. A summary is included in Section 6. Reference
27、s, a Glossary, and a Bibliography follow the summary. Information for this review was gathered in three ways. First, several computer databases were searched for information related to the toxicity of the common ions (listed above) to aquatic organisms. Those databases included AQUIRE, Biosis Previe
28、ws“, Cornpendex, Oceanic Abstracts, Aquatic Science Abstracts, CAB Abstracts, Inside Conferences, Wilson Applied Science and Technology Abstracts, Water Resources Abstracts, WATERNET“, GEOBASE“, IAC Newsletter DB“, Enviroline, Pollution Abstracts, Environmental Bibliography, and SciSearch“. Second,
29、a manual literature search was conducted to gather information that might not be found in the databases. Finally, there was direct communication with researchers involved in ion toxicity studies. TOTAL DISSOLVED SOLIDS IN WET TESTS Recent studies have shown that toxicity in effluents from many diffe
30、rent sources can be attributed to major ions. Many of these ions occur naturally in receiving streams and do not pose the bioaccumulative risk that some other toxicants do. Elevated ion levels occur in some industry source waters and WET toxicity may therefore be artifactual and not a true reflectio
31、n of effluent toxicity resulting from a manufacturing or treatment process. Nevertheless, there are few regulatory guidelines specifically designed to address TDS ion toxicity. Many states have limits on TDS or a few TDS ions (principally CI- and SO,-). But compliance with existing water quality dis
32、charge criteria or state standards does not guarantee that an effluent will not be toxic. In addition, few permits require analysis of a full suite of ions. Measurement of limited parameters such as TDS, CI-, and SO,- would be insufficient to determine if toxicity were due to an unmeasured single io
33、n. There is no national policy for addressing TDS toxicity issues. A survey conducted of all state and USEPA regions indicated that many states have not experienced problems with TDS, although unexplained episodes of toxicity might be attributable to TDS. Only three states and two USEPA regions were
34、 identified that have established some current or proposed procedural guidance for dealing with TDS toxicity; those are described in the following sections. Table 1-1 provides a list of individuals who can provide information from states and EPA regions about TDS and toxicity related to TDS. Additio
35、nal information on the role of TDS and ion imbalance in toxicity testing may be found in Goodfellow et a/. (In Preparation). USEPA Reaions 9 and 10 USEPA Regions 9 and 10 recognized that TDS ions in effluent can cause toxicity and confound efforts to identify the causative toxicant(s). As a general
36、guide, it is suggested that if conductivity exceeds 3,000 and 6,000 pmhoskm at the LC, for Ceriodaphnia dubia and Pimephales promelas (fathead minnow), respectively, then TDS toxicity should be considered (USEPA, 1996). In order to quantify the impacts of TDS, an effluent sample should be thoroughly
37、 characterized relative to the ions in the sample. Once this characterization is completed, a computer model (the GRI-FWSTP program, Tietge et al., 1994) can be used to predict toxicity. Mock effluent tests are also an important part of the confirmation process. Colorado The Colorado Department of P
38、ublic Health and Environment (CDPHE) Water Quality Control Division (Division) has prepared a draft revision of its ?Whole Effluent Toxicity Permit Implementation Guidance Document? that specifically addresses IDS as a toxicant. Although this document remains in draft form (as of this writing), perm
39、ittees can follow the procedures to identify and address toxicity due to TDS ions. The guidelines state that, if a TIE rules out other toxicants, except TDS, then the permittee can provide the Division with 1) effluent analytical chemistry, 2) results of an effluent WET test, and 3) results of a moc
40、k effluent WET test. If acute toxicity is of concern, then the Division will use a computer program (the GRI-FWSTP program, Tietge et a/. , 1994) to complement existing WET data. If the acute WET test is passed using Daphnia magna (which is more tolerant than C. dubia to TDS ions), then the permitte
41、e may request a permit amendment to change WET test species. If D. magna cannot tolerate the elevated TDS, or if the required test is chronic, permittees may be required to conduct an Aquatic Impairment Study (AIS) of the receiving stream. A CDPHE AIS includes the collection of in situ biological, c
42、hemical, and physical data and incorporates some of the methods described in the USEPAs Rapid Bioassessment Protocols (Plafkin et al., 1989). Following the AIS, WET tests may be modified to switch species or remove TDS (if possible). Additional mitigation measures also may be needed. 1-3 _ STD*API/P
43、ETRO PUBL 4bbb-ENGL L999 0732270 0636337 837 M Table 1-1. State and Regional Contacts Regarding TDS Toxicity Questions. Name Phone Affiliation Madonna Narvaez (206) 553-1 774 USEPA Regional Office (Region IO) in Seattle Marion Bertolotti (334) 260-2748 Alabama Department of Environmental Management
44、Arkansas Department of Pollution Control and Ecology, NPDES Branch Biomonitoring Branch Bernie Finch Nat Nehus (501) 682-0744 (501) 682-0663 Linda Taunt (602) 2074665 Arizona Department of Environmental Quality, Water Pemits Victor de Vlaming Bruce Gwynne William Rodriguez Tuck Vath Peter Otis Lila
45、Tang Brad Hagemann Dennis Dasker Valerie Connor Bruce Warden Orlando Gonzalez Hope Smythe Bruce Posthumus (916) 657-0795 (707) 576-2661 (707) 576-2863 (707) 576-2699 (707) 576-2662 (510) 622-2300 (805) 549-3697 (323) 266-7518 (916) 255-31 I1 (530) 542-541 6 (760) 776-8962 (909) 782-4493 (61 9) 467-2
46、964 California State Water Resource Control Board, Division of Water Quality California Regional Water Quality Control Board, North Coast Region California Regional Water Quality Control Board, North Coast Region California Regional Water Quality Control Board, North Coast Region California Regional
47、 Water Quality Control Board, North Coast Region California Regional Water Quality Control Board, San Francisco Bay Region California Regional Water Quality Control Board, Central Coast Region California Regional Water Quality Control Board, Los Angeles Region California Regional Water Quality Contr
48、ol Board, Central Valley Region California Regional Water Quality Control Board, Lahontan Region California Regional Water Quality Control Board, Colorado Basin California Regional Water Quality Control Board, Santa Anna Region California Regional Water Quality Control Board, San Diego Region Robert
49、 McConnell (303) 692-3578 Colorado Department of Public Health and Environment Lee Dunbar (860) 424-3731 Connecticut Department of Environmental Protection Rick Greene (302) 739-4590 Delaware Department of Environmental Quality, mce of Water Resources Steve Wolfe (850) 921-9830 Florida Department of Environmental Protection, Biology Section 1-4 STD-API/PETRO PUBL State or Region GA HI IA ID IL IN KS KY LA MA MD ME MI MN MO MS MT NC ND NE NH NJ NM 4bbb-ENGL 1999 Name Phone Affiliation Susan Salter (404) 362-2680 Georgia Environmental Protection Division
