METHOD FOR VALIDATION OF SITE-SPECIFIC WATER QUALITY CRITERIA OF RIVER BASIN

Abstract

A method for validation of site-specific water quality criteria of a river basin includes steps of: analyzing the biota distribution characteristics of a river basin; eliminating non-resident related species from the toxicity database of target pollutants; supplementing toxicity values of site-specific resident sensitive species and endemic species; establishing a resident toxicity database for the river basin; comparing the degrees of fitting of species sensitivity distribution (SSD) models and identifying the optimal SSD model; and validating the water quality criterion value to complete the derivation and validation of the site-specific water quality criteria of the river basin. The method can improve the nativeness of the site-specific water quality criteria of the river basin, be used for the formulation of the site-specific water environment quality standards of the river basin, and provide support for the water quality management of the river basin.

Claims

1. A method for validation of site-specific water quality criteria of a river basin, wherein the method comprises the following steps: step 1: analyzing the biota distribution characteristics of a river basin; step 2, eliminating non-resident related species from the existing toxicity values; 2.1) collecting, screening and summarizing the aquatic toxicity values of target pollutants; 2.2) comparing the resident species with the biological species having toxicity values in the river basin; 2.3) marking the species completely corresponding to the species names; 2.4) marking and reserving the species with different species names and the same species level based on biological classification as the reference; 2.5) eliminating the species that do not meet the requirements in steps 2.3) and 2.4); step 3, supplementing toxicity values of site-specific resident sensitive species and endemic species; 3.1) screening the toxicity values of the species, wherein the screening principle is: the toxicity test subjects and the test process required to obtain toxicity values meet the requirements of the relevant toxicity test specifications, and after all qualified toxicity values of the species are screened, the species mean acute values SMAV of the finally reserved species in step 2 are calculated and sorted from small to large, and the calculation formula of the SMAV is as follows: $SMAV=\sqrt[n]{E{C}_{501}\times E{C}_{502}\times E{C}_{503}\times \mathrm{.Math.}\times {\mathrm{EC}}_{50n}}$ wherein EC.sub.501˜EC.sub.50n are the toxicity values of the same species, and n is the number of toxicity values of the same species; and EC50 can be substituted by median lethal concentration LC50; 3.2) selecting four species with the minimum SMAVs, and identifying four sensitive test species corresponding to four families according to the biological taxonomy of the species; in principle, each family corresponds to one species, but if no available test species exists in a family, amplifying one species from the higher sensitive family or identifying one substitute species from the families under sorting; 3.3) based on the family corresponding to the species with the minimum SMAV, identifying two endemic test species among the endemic species in the river basin; 3.4) conducting toxicity tests on the sensitive test species identified in step 3.2) and the endemic test species identified in step 3.3), and setting control tests for the toxicity tests, wherein the test species, exposure conditions and test procedures of the control group and the experimental group shall be exactly the same, the exposure concentration shall be set based on the principle of equal ratio, and the SPSS linear regression method is used to calculate EC50 or LC50 as the supplementary toxicity value; step 4, establishing a resident toxicity database for the river basin; 4.1) if the sensitive test species already has a toxicity value, using the newly obtained toxicity value to replace the original toxicity value of the species; 4.2) adding the sensitive test species without previous toxicity values and the toxicity values of endemic test species to the original toxicity database; 4.3) according to the toxicity values, sorting all the species in ascending order to form the resident toxicity database of the river basin; step 5, comparing the degrees of fitting of species sensitivity distribution SSD models and identifying the optimal SSD model; 5.1) calculating the cumulative probability P of the species; 5.2) taking all base-10 natural logarithmic values as toxicity values; 5.3) with the logarithm values of the toxicity values as independent variables and the cumulative probabilities of the species as dependent variables, respectively using normal, logistic and BurIII distribution models for fitting to obtain three different fit coefficients R.sup.2; and using the final fitting model derived with the maximum fit coefficient R.sup.2 as the criterion as the optimum SSD model; step 6, validating the water quality criterion value; 6.1) with the logarithm value of the toxicity value in the resident toxicity database of the river basin determined in step 4 as the X variable and the cumulative probability of the species as the Y variable, adopting the fitting models identified in step 5.3) for fitting; 6.2) taking the X value corresponding to Y=0.05 for base-10 exponent transformation and then dividing by the safety coefficient M to obtain that the site-specific water quality criterion value of the river basin of the target pollutant is 10.sup.X/M; 6.3) based on the toxicity percentage sorting method, calculating the final toxicity value FV by using the toxicity values of four most sensitive species among the resident species and the sensitive species, and dividing the FV obtained by derivation by the safety coefficient to obtain the site-specific water quality criterion of the river basin, wherein the calculation formula of the final toxicity value is as follows: $\begin{array}{cc}{S}^2=\frac{.Math.\left[{\left(\ln \mathrm{SMAV}\right)}^2\right]-\left[{\left(.Math.\ln \mathrm{SMAV}\right)}^2/4\right]}{.Math.\left(P\right)-\frac{{\left[.Math.\left(\sqrt{P}\right)\right]}^2}{4}}L=\left\{.Math.\left(\ln \mathrm{SMAV}\right)-S\left[.Math.\left(\sqrt{P}\right)\right]\right\}/4A=S\left(\sqrt{0.05}\right)+LFV=e^A& \end{array}$ wherein S, L and A are respectively the parameters generated in the calculation process, SMAV is the species mean acute value, P is the cumulative probability corresponding to the species, and FV is the final toxicity value; 6.4) according to the resident sensitive species and the sorting of the toxicity of the sensitive species in the site-specific resident toxicity database, respectively selecting the weight values obtained by two different derivation methods; TABLE-US-00005 TABLE 1 Ranges of Average Cumulative Probabilities of Resident Sensitive Species and Endemic Species 0-0.30 0.31-0.50 0.51-0.80 0.81-1.0 Weight value obtained based 0.3 0.5 0.8 1.0 on species sensitivity method Weight value obtained based 0.7 0.5 0.2 0.0 on toxicity sorting method according to the weight values in the table above, obtaining the site-specific water quality criterion value of the river basin, as shown in the following formula:
WQC=WQCs×a+WQCr×b wherein WQC is the final site-specific water quality criterion value of the river basin, WQCs is the site-specific water quality criterion value of the river basin derived by the species sensitivity method, WQCr is the site-specific water quality criterion value of the river basin derived by the toxicity sorting method, a is the weight value obtained based on the average cumulative probability of the resident sensitive species, and b is the weight value obtained based on the average cumulative probability of the endemic species.

2. The method for validation of site-specific water quality criteria of a river basin according to claim 1, wherein step 1 is specifically as follows: 1.1) collecting the fauna and local literature yearbooks of the river basin and summarizing species categories in the river basin; 1.2) sorting all site-specific species in order of genus, family and order from low to high according to biological taxonomy levels; 1.3) marking the endemic species according to the biological distribution characteristics of the river basin in combination with the data query of the species distribution area; 1.4) summarizing the biota distribution characteristics of the river basin.

3. The method for validation of site-specific water quality criteria of a river basin according to claim 1, wherein the ratio in the principle of equal ratio in step 3.4) is 2.

4. The method for validation of site-specific water quality criteria of a river basin according to claim 1, wherein the calculation method for the cumulative probability P of the species in step 5.1) is as follows: the species with the minimum toxicity value is assigned a value of 1, by analogy, the species with the maximum toxicity value is assigned a value of n, a total of n species are assumed, and the cumulative probability of the species is P=r/n+1, wherein n is the number of the species in sorting.

5. The method for validation of site-specific water quality criteria of a river basin according to claim 1, wherein the safety coefficient R in step 6.2) is 2.

Description

DESCRIPTION OF DRAWINGS

[0047] FIG. 1 is a flow chart of validation of site-specific water quality criteria of a river basin of the present invention.

[0048] FIG. 2 shows a sensitivity distribution curve of aquatic species in Liaohe River Basin in embodiments of the present invention.

DETAILED DESCRIPTION

[0049] The present invention relates to a method for validation of site-specific water quality criteria of a river basin, which is suitable for validation of site-specific water quality criteria of river basins that have water quality indexes of the national water quality criteria.

[0050] The present invention will be further described in detail below in combination with specific embodiments.

[0051] The validation process of ammonia nitrogen water quality criteria of Liaohe River Basin in China is as follows.

[0052] Step 1: analyzing the biota distribution characteristics of a river basin; Collecting the databases of Fauna Sinica, Liaoning Fauna, and China National Knowledge Infrastructure (CNKI), summarizing the distribution information of aquatic species in Liaohe River Basin, and classifying and summarizing the collected distribution information of aquatic species in Liaohe River Basin in order of species, genus and family based on biological classification. According to the available data, in terms of aquatic species, about 96 species of vertebrates and 291 species of invertebrates are distributed in Liaohe River Basin.

[0053] Step 2, eliminating non-resident related species from the existing toxicity values; Collecting aquatic toxicity values with ammonia nitrogen as the target pollutant, including toxicity database (ECOTOX) and ammonia nitrogen water quality criterion derivation guideline of the United States Environmental Protection Agency (USEPA), database of China National Knowledge Infrastructure (CNKI), Google Scholar and other data sources. Ammonia nitrogen aquatic toxicity values covering about 120 species are collected; after eliminating species by comparing the aquatic biota distribution characteristics of Liaohe River Basin, a total of 25 aquatic species with native correlation with Liaohe River Basin are screened, wherein 16 species are distributed in Liaohe River Basin and the other 9 species are substitute species, i.e., the species are not distributed in Liaohe River Basin, but the species of the same family as the corresponding species are distributed in Liaohe River Basin. See Table 1.

TABLE-US-00002 TABLE 1 Toxicity Database of Existing Species in Liaohe River Basin (all toxicity values are based on the conditions of pH = 7.0 and temperature = 20° C.) Species in Species Mean Liaohe River Substitute Acute Value Order Species Family Basin Species* (mg/L) 1 Leuciscus cephalus Cyprinidae Yes 40.9 2 Acipenser sinensis Acipenseridae Yes 44.6 3 Mylopharyngodon piceus Cyprinidae Yes 57.2 4 Corbicula fluminea Cyrenidae Yes 62.1 5 Rana pipiens Ranidae Yes 96.4 6 Daphnia pulicaria Daphniidae Yes 99 7 Cyprinus carpio Cyprinidae Yes 106.3 8 Eriocheir sinensis Varunidae Yes 112.9 9 Ceriodaphnia dubia Daphniidae Yes 134.2 10 Simocephalus vetulus Daphniidae Yes 142.9 11 Acipenser brevirostrum Acipenseridae Yes 156.7 12 Cyclops strenuus Cyclopidae Yes 162.2 13 Physa gyrina Physidae Yes 164.5 14 Daphnia magna Daphniidae Yes 164.8 15 Tubifex Tubificidae Yes 216.5 16 Cottus bairdii Cottidae Yes 222.2 17 Limnodrilus hoffmeisteri Tubificidae Yes 241.5 18 Anguilla Anguillidae Yes 286 19 Macrobrachium nipponense Palaemonidae Yes 366.7 20 Drunella grandis Ephemerellidae Yes 442.4 21 Rana chensinensis Ranidae Yes 461.2 22 Cipangopaludina cathayensis Viviparidae Yes 532.1 23 Chironomus tentans Chironomidae Yes 546.2 24 Misgurnus anguillicaudatus Cobitidae Yes 784.9 25 Chironomus riparius Chironomidae Yes 1029 *Substitute species: the species are not distributed in Liaohe River Basin, but the species of the same family are distributed in Liaohe River Basin.

[0054] Step 3, supplementing toxicity values of site-specific resident sensitive species and endemic species;

[0055] After sorting the species in Table 1 according to the toxicity values, determining the four most sensitive families to ammonia nitrogen in Liaohe River Basin as: Cyprinidae, Acipenseridae, Cyrenidae and Ranidae. The process of determining sensitive species is as follows: for Cyprinidae, selecting Cyprinus carpio, as the species of Acipenseridae belong to protected animals, adding a test species, Pseudorasbora parva, to Cyprinidae; for cyrenidae, selecting Corbicula fluminea; as the species of Ranidae are amphibian and have poor laboratory availability, skipping to Daphniidae in the order of Table 1, and selecting Daphnia magna; and at this point, four sensitive test species are determined as Cyprinus carpio, Pseudorasbora parva, Corbicula fluminea and Daphnia magna.

[0056] According to Table 1, the most sensitive family of species in Liaohe River Basin is Cyprinidae, and according to the aquatic biota distribution characteristics of Liaohe River Basin, Abbottina liaoningensis and Ctenogobius giurinus are determined as endemic test species in Liaohe River

[0057] According to the step requirements of experiment guidelines in ASTM E1193-97 and ASTM E729-96, testing the above four sensitive test species and two endemic species for toxicity, and counting the number of deaths in each experimental group within 96 h for four species of tested fish; and counting the number of deaths in each experimental group within 48 h for two species of invertebrates, and calculating the median lethal concentration of the species based on the above experimental results.

[0058] With a species a as an example (in case of exposure to six different concentration series, each group is exposed to three parallel concentrations), calculating the toxicity value in the following process:

[0059] {circle around (1)} Counting the number of deaths of each experimental group of the species a under different exposure concentrations at the end of the toxicity test, and forming Table 2 through summarization;

TABLE-US-00003 TABLE 2 Summary of Deaths of Each Experimental Group of Species a under Different Exposure Concentrations Exposure Concentration Death Initial Number C1 S1 N C1 S2 N C1 S3 N . . . . . . . . . C6 S16 N C6 S17 N C6 S18 N

[0060] {circle around (2)} Copying the three columns of data in Table 2 to SPSS software, selecting the three columns of data, clicking “Analysis”-“Regression”-“Probit”, selecting “Exposure Concentration” into the “Covariate” column, “Death” into the “Response Frequency” column and “Initial Number” into the “Summary of Observed Values” column, selecting “Log base is 10” in the “Transform” column, leaving the other options as the default, and clicking “OK”;

[0061] {circle around (3)} According to the SPSS output, determining the exposure concentration corresponding to a probability of 0.500 as the median lethal concentration LC50 of the species a.

[0062] According to the above process, determining the median lethal concentration LC50 of the six test species, that is the toxicity values of the six test species.

[0063] Step 4, establishing a resident toxicity database for the river basin;

[0064] Based on the supplementary toxicity values of six species and the existing toxicity database, replacing the toxicity values of Cyprinus carpio, Corbicula fluminea and Daphnia magna, and then supplementing the resident toxicity values of Pseudorasbora parva, Abbottina liaoningensis and Ctenogobius giurinus. As a result, the establishment of the resident toxicity database of ammonia nitrogen in Liaohe River Basin is completed, and all the species mean acute values are transformed to base-10 logarithmic values.

[0065] Step 5, comparing the degrees of fitting of species sensitivity distribution (SSD) models and identifying the optimal SSD model;

[0066] 5.1) Calculating the cumulative probability of each species, wherein the calculation method is as follows: all the species are sorted in ascending order based on the species mean acute values, the serial number r of the species Leuciscuscephalus with the minimum toxicity value is 1, by analogy, the serial number of the species Chironomus riparius with the maximum toxicity value is 28, and the cumulative probability of the species is P=r/28+1, wherein 28 is the number of the species in sorting.

[0067] 5.2) Transforming the species mean acute values of all the species to base-10 logarithms, wherein the final form is shown in Table 3.

TABLE-US-00004 TABLE 3 Resident Toxicity Database of Ammonia Nitrogen in Liaohe River Basin (all toxicity values are based on the conditions of pH = 7.0 and temperature = 20° C.) Species Mean Acute Value Cumulative Log.sub.10 Order Species Family (SMAV) Probability (SMAV) 1 Leuciscus cephalus Cyprinidae 40.9 0.03 1.61 2 Acipenser sinensis Acipenseridae 44.6 0.07 1.65 3 Abbottina liaoningensis Cyprinidae 45.2 0.10 1.66 4 Mylopharyngodon piceus Cyprinidae 57.2 0.14 1.76 5 Ctenogobius giurinus Gobiidae 61.5 0.17 1.79 6 Corbicula fluminea Cyrenidae 73.1 0.21 1.86 7 Cyprinus carpio Cyprinidae 85.7 0.24 1.93 8 Rana pipiens Ranidae 96.4 0.28 1.98 9 Daphnia pulicaria Daphniidae 99 0.31 2.00 10 Daphnia magna Daphniidae 100.1 0.34 2.00 11 Eriocheir sinensis Varunidae 112.9 0.38 2.05 12 Pseudorasbora parva Cyprinidae 116.2 0.41 2.07 13 Ceriodaphnia dubia Daphniidae 134.2 0.45 2.13 14 Simocephalus vetulus Daphniidae 142.9 0.48 2.16 15 Acipenser brevirostrum Acipenseridae 156.7 0.52 2.20 16 Cyclops strenuus Cyclopidae 162.2 0.55 2.21 17 Physa gyrina Physidae 164.5 0.59 2.22 18 Tubifex tubifex Tubificidae 216.5 0.62 2.34 19 Cottus bairdii Cottidae 222.2 0.66 2.35 20 Limnodrilus hoffmeisteri Tubificidae 241.5 0.69 2.38 21 Anguilla anguilla Anguillidae 286 0.72 2.46 22 Macrobrachium nipponense Palaemonidae 366.7 0.76 2.56 23 Drunella grandis Ephemerellidae 442.4 0.79 2.65 24 Rana chensinensis Ranidae 461.2 0.83 2.66 25 Cipangopaludina cathayensis Viviparidae 532.1 0.86 2.73 26 Chironomus tentans Chironomidae 546.2 0.90 2.74 27 Misgurnus anguillicaudatus Cobitidae 784.9 0.93 2.89 28 Chironomus riparius Chironomidae 1029 0.97 3.01

[0068] 5.3) {circle around (1)} Copying the two columns of data including the cumulative probability of the species and the log-transformed toxicity value into Origin software, and selecting the cumulative probability of the species as “Y” and the log-transformed toxicity value as “X”;

[0069] {circle around (2)} Selecting the two columns of data “X” and “Y”, clicking “Plot”-“Symbol”-“Scatter”, then left clicking to select the generated dot plot, continuing to click “Analysis”-“Fitting”-“Nonlinear Curve Fit”, and using three function models normal, logistic and BurrIII for fitting, wherein the three functional relations are as follows:

[0070] The functional relation of the normal model is y=(1/(a*(2π){circumflex over ( )}0.5))*exp((−(x−b){circumflex over ( )}2)/(2*a{circumflex over ( )}2));

[0071] The functional relation of the logistic model is y=1/exp(−(x−a)/b);

[0072] The functional relation of the BurrIII model is y=1/(1+(1+a/x){circumflex over ( )}b){circumflex over ( )}c;

[0073] Using the above three functional relations for nonlinear fitting to obtain three different fit coefficients R.sup.2.

[0074] {circle around (3)} Comparing the fit coefficients, and selecting the model with the best fitness as the optimal SSD model.

[0075] After nonlinear fitting, the normal distribution fit coefficient R.sup.2 is 0.9315, the logistic distribution fit coefficient R.sup.2 is 0.9887, and the BurIII distribution fit coefficient R.sup.2 is 0.3265. The logistic model is determined as the optimal SSD model.

[0076] Step 6, validating the water quality criterion value.

[0077] {circle around (1)} Using the logistic model for nonlinear fitting of data, and based on the fitting curve (FIG. 2), using Y=0.05 to obtain X=1.4302;

[0078] {circle around (2)} Transforming the obtained X value to a base-10 exponent to obtain a value of 26.93 mg/L, and dividing this value by the safety coefficient 2 to obtain that the ammonia nitrogen water quality criterion value of Liaohe River Basin derived by the species sensitivity method is 13.47 mg/L.

[0079] {circle around (3)} Based on the toxicity percentage sorting method, using the toxicity values of four most sensitive species among the resident species and the sensitive species, wherein the four most sensitive species of resident sensitive species and endemic species in Liaohe River Basin are Abbottina liaoningensis, Ctenogobius giurinus, Corbicula fluminea and Cyprinus carpio, and based on the formula, obtaining that the ammonia nitrogen water quality criterion value of Liaohe River Basin derived by the toxicity sorting method is 15.91 mg/L.

[0080] {circle around (4)} The average cumulative probability of resident sensitive species and endemic species in Liaohe River Basin is 0.245 which is between 0 and 0.3, so the weight value obtained by the species sensitivity method is selected as 0.3, and the weight value obtained by the toxicity sorting method is selected as 0.7, thereby obtaining that the ammonia nitrogen water quality criterion value of Liaohe River Basin is 13.47×0.3+15.91×0.7=15.18 mg/L, which is the validation value for the ammonia nitrogen water quality criteria of Liaohe River Basin (under the conditions of pH=7.0 and temperature=20° C.), and the validation of the ammonia nitrogen water quality criteria of Liaohe River Basin is completed.

[0081] The above embodiments only express the implementation of the present invention, and shall not be interpreted as a limitation to the scope of the patent for the present invention. It should be noted that, for those skilled in the art, several variations and improvements can also be made without departing from the concept of the present invention, all of which belong to the protection scope of the present invention.