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    TECHNICAL REPORT







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                  COASTAL PROGRAM

                SEDIMENT CHEMISTRY
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                     BASELINE STUDY







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       571
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       1991
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            MA DEPARTMENT OF ENVIRONMENTAL MANAGEMENT
          ~qt~q7~q-~q.~q&~q-~q-~q*~q.~q.~q;~92qONG. W. L. DICKINSON DRIVE ~28qo MONTGOMERY, AL 36130
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                           A SEDIMENT CHEMISTRY BASELINE STUDY
                                   OF COASTAL ALABAMA













                                            By:

                                      Gary L. Halcomb

                                      Coastal Program
                    Alabama Department of Environmental Management
                                   2204 Perimeter Rd.
                                     Mobile, Alabama













                                       November 1991












                                      US Department of Commerce
                                  NOAA Coastal Services Conter Library
                                       2234 South Hobson Avenue
                                       Charleston, SC 29405-2413




































                                      DISCLAIMER




         The mention of t--ade names or brand names in this document is for

      illustrative purposes only and does not constitute an endorsement by the

       Alabama Department of Environmental Management, the Alabama Department

           of Economic and Community Affairs or the National Oceanic and

                            Atmospheric Administration.












                                     TABLE OF CONTENTS



               Acknowledgments   ......................................  II

               List of Figures and Tables   ...........................  III

               Executive Summary    ...................................    1

               Introduction   ..........................................   3


               Materials and Methods   .................................   8


               Results   ............................................... 12


               Discussion   ............................................ 25


               Conclusion   ...........................................  28

               Bibliography  ........................................    29

               Appendix A: Normal scores vs metal values, all sample sites.

               Appendix B: Metal vs Aluminum values, all sample sites.

               Appendix C: Normal scores vs metal values, clean sites.

               Appendix D: Metal vs Aluminum values, clean sites.













                                   ACKNOWLEDGEMENTS




           This report was funded in part by the Alabama Department of

      Economic and Community Affairs, Office of the Governor of the State of

      Alabama; and in part by a grant from the Office of Ocean and Coastal

      Resources Management, National Oceanic and Atmospheric Administration,

      United States Department of Commerce.    The author wishes to express his

      kindest appreciation to Carolyn Merryman, David Wigger and Clinton

      Townsend of the ADEM Mobile Branch Laboratory for their diligence and

      many long hours spent processing and analyzing the samples.       Thanks

      also to Mark Register, Nancy Van Antwerp, Michael Boyle, Al Hickey and

      Kelly Williams for their invaluable assistance collecting the samples.

      Regards also are extended to Dr. Steven Schropp, Dr. Herbert Windom

      and Dr. Wayne Isphording for their advice and technical assistance in

      preparing this paper.













                                 LIST OF TABLES AND FIGURES



             Table 1: Station   locations, latitudes and longitudes       ....... 11

             Table 2:  Probability plot coefficients for normality of
                       metals data    .......................................     15


             Table 3:  Correlation coefficients for metals vs aluminum         ... 16

             Table 4:  Results of regression analyses using aluminum as the
                       independent variable and other metals as dependent
                       variables    .........................................     17


             Table 5:  Sediment metals data     ..............................    18

             Table 6:  Probability plot coefficients for normality of
                       metals data, "clean" sites data       ...................  22

             Table 7:  Correlation coefficients for metals vs aluminum,
                       clean" sites data     .................................    23

             Table 8: Results of regression analyses using aluminum as the
                       independent variable and other metals as dependent
                       variables, "clean" sites data      .....................   24

             Figure 1: Locations of sample stations       .....................   10

             Figure 2: Test case, lead in sediment at Station DR-1         ...... 27










                                   EXECUTIVE SUMMARY




            This report details the application of the concept of utilizing

      aluminum as a "normalizing factor" for interpreting metals data in

      coastal sediments. Accurate interpretation of such information is often

      complicated by the various factors influencing metals concentration in

      sediments.    These factors may be natural, like the geology of the

      drainage basin and sediment grain size to name a couple, or they may be

      anthropogenic such as wastewater discharges from industrial processes,

      development of offshore hydrocarbon resources and shipyard activity.

      Utilization of aluminum as a so-called "geochemical normalizer" allows

      for an accounting of the natural variability of metals in sediments and

      for the identification of sediments enriched with metals relative to


      expected natural concentrations.



            The principle of utilizing aluminum as a "normalizing factor" is

      based on the constant relationships existing between metals and aluminum

      in the earth's crust and in natural sediments. This concept has been

      successfully employed by investigators in other states for developing a

      method for identifying anthropogenic enrichment of coastal sediments.



            Samples of sediments from coastal Alabama were collected and

      analyzed    for their     metals content.      Metal/aluminum regressions,

      correlations and prediction limits were calculated and graphical plots

      of these     relationships were     constructed.    The   results indicate

      statistically significant relationships between aluminum and eight

      other metals. Metals data from coastal sediments can now be plotted on








      these diagrams of the relationships assessed to determine if the metals

      content of the sample is within natural ranges or represents an enriched


      area.




           The efforts of this study accomplished several objectives, these

      being: 1) verifying the validity of applying the concept of aluminum as

      a "normalizing factor" for the sediments of coastal Alabama, 2) defining

      metal/aluminum relationships for "clean" sediments in coastal Alabama,

      3) tentitive identification of areas of potentially enriched sediments,

      and 4) incorporation of a thorough and comprehensive Q&A program

      evaluating performance of the laboratory through use of reference

      standards and participation in an intercalibration exercise.

































                                           2











                                     INTRODUCTION




            The estuaries of coastal Alabama have become subjects of increasing

      concern    relative    to   environmental stresses     from     developmental

      activities.    These stresses may be in the form of industrial and

      municipal wastewater discharges, urban non-point sources, agricultural

      runoff, dredging and port and marina development.            Of particular

      interest is the potential of these activities for enriching aquatic

      environments with heavy metals.



           The sources of heavy metal enrichment are numerous and varied.

      These sources range in size from metal plating shops discharging small

      quantities on an intermittant basis to large facilities discharging

      millions of gallons daily of treated wastewater containing various heavy

      metals.    Lead from the exhaust emissions of engines burning leaded

      gasoline also ends up in aquatic environments as a result of atmospheric

      deposition and direct input from boat motors. Additional sources common

      to coastal areas include the marine paints and surface coatings utilized

      in the     shipbuilding industry.     These preparations,     designed for

      protection against corrosion and inhibition of the growth of fouling

      organisms, are based on heavy metal formulations toxic to many species

      of estuarine life. The uncontrolled release of these materials from the

      removal of old paint by sandblasting and the spray application of new

      coatings has, over the years, been a long standing source of metal

      enrichment to aquatic environments. A more recent and controversial

      source of potential enrichment of metals in the environment has been the

      development of offshore hydrocarbon reserves.         The exploration and



                                             3








      production   activities    characterizing    offshore   development     are

      accompanied by the use of clay-based drilling fluids and the generation

      of considerable quantities of geological formation cuttings from the

      well hole. The resultant waste drilling fluids and cuttings are rich in

      metals not common to estuarine sediments. The uncertain potentials for

      adverse impacts to aquatic ecosystems from these numerous sources have

      prompted federal and state regulatory agencies to examine more closely

      the effects of metal enrichment on sediment quality.



           Consequently, needs have arisen for the investigation of the metal

      content of sediments throughout the Alabama coastal area.          Specific

      needs from A regulatory perspective are:

                1. Determination of "backround" levels of metals in sediments


                of the entire coastal area, or in other words the

                concentrations of metals atttributable to natural causes.

                2. Development of a "standardized" method for sampling and

                analyzing sediments and interpreting the data for meaningful

                results.


                3. Application of a "standardized" method along with a

                database of natural levels of metals in sediments in order to

                ascertain the degree of metal enrichment resulting from

                anthropogenic sources.

                4. Identification of potential   "hot spots" or areas of highly

                enriched sediments which may constitute a hazard to aquatic

                life and may require remediation.



           Previous studies of sediment chemistry in coastal Alabama, Malatino



                                            4








       (1980) and Isphording (1985 and 1987), delt with Mobile Bay and

       Mississippi Sound but did not examine the smaller estuaries or tributary

       streams. Although these previous studies generated a useful database

       for future reference of metals in sediments the investigators did not

       delve into developing a standardized method for identifying polluted

       sediments.




           Schropp and Windom (1988) and Windom et al (1989) examined metal

       concentrations in estuarine sediments from coastal Florida and Georgia

       and develoDed a method for      identifying metal enrichment due to

       anthropogenic activities.   This method is based on the naturally

       occurring relationships between aluminum and other metallic elements.

       These relationships allow for the identification of polluted sediments

       by using aluminum as a reference element. The basis for this method is

       that aluminum occurs naturally in all estuarine sediments and the

       concentrations of other metals tend to vary with the concentration of

       aluminum. These naturally occuring proportions of metals relative to

       aluminum have been reported by several investigators (r"Lurekian and

       Wedepohl, 1961; Taylor, 1964; Duce et al, 1976) to be fairly constant.

       This allows for the use of aluminum as a reference element or

       "normalizing factor" for identifying sediments enriched by anthropogenic

       activities. This concept has been used to examine metal pollution in

       the Savannah River estuary (Goldberg, 1979) and lead pollution in the

       Mississippi River (TrefLev et al, 1985).



           Although the principle of      using aluminum as a "geochemical

       normalizer" was successfully employed in the above mentioned studies



                                           5








      it cannot be assumed that this applies to coastal Alabama.     The geology

      of the drainage basins of the study area is characterized by clays

      exceptionally rich in aluminum (Isphording, pers. comm.) which could

      skew the statistical distribution of aluminum data.           A non-normal

      distribution of such data complicates interpretation of results making

      reliable determinations of contaminated areas a difficult task (Sokal

      and Rohlf, 1969; Schropp and Windom, 1988). Other metallic elements,

      barium for example, are also naturally abundant in the clays of the area

      (Isphording, pers. comm.), these too might compound the difficulty of

      identifying    anthropogenically enriched     sediments.    An    additional

      complicating factor for Mobile Bay is the history of releases of

      aluminum enriched clays and stormwater runoff from the tailings ponds of

      an aluminum extraction facility previously operated in Mobile by The

      Aluminum Company of America. Although this facility has not operated in

      nearly a decade, stormwater runoff and the loss of spent bauxite ore

      from breaches in the walls of the tailings ponds have contributed some

      enrichment, albeit of an unknown magnitude and significance, to the

      lower Mobile River and Mobile Bay.



            .. his study applied the concept      of utilizing aluminum as a

      no-rmalizing factor to metal concentrations in sediments of coastal

      Alabama.    The goal of this effort being a standardized method for

      sampling, analyzing and objectively        interpreting metals data for

      sediments. Tn acheiving that goal a valuable database was compiled and

      preliminary identification of enriched areas was accomplished.



           The results indicated that aluminum does account for most of the




                                             6








      variability of other metals except mercury.   The scarcity of natural

      sources of mercury in the drainage basins of the study area would appear

      to account for this lack of covariance (Isphording, pers.      comm.;

      cchropp, pers. comm.).


















































                                         7











                                   MATERIALS AND METHODS



             Sediment samples (cores) were collected from 53 stations in coastal

       Alabama (Figure 1), the latitude and longitude coordinates of these

       stations are given in Table 1. The sites sampled encompassed a wide

       variety of sediment types ranging from aluminum and iron rich clays of

       the Mobile River Delta and upper Mobile Bay to the coarse grained silica

       rich sands of lower Perdido Bay.         A K-B type core sampler (Wildlife

       Supply     Co.,      cat.      no.        2402-A12)     equipped       with      a

       cellulose-acetate-butyrate liner tube was used for retrieval of sediment

       samples from sites where the water depth was greater than one meter;

       where the water depth was less than one meter samples were collected by

       utilizing the liner tubes as hand core samplers. The upper five

       centimeters of each core was placed in a clean glass jar and capped with

       a teflon lined lid.      Samples were collected in triplicate, two samples

       for immediate processing and the third sample was "archived" in a

       ireezer for future analyses in case of widely varying results between

       the first two.




            Preparation of sediments for analyses began with oven drying

       samples at 60*C followed by weighing out a 0.25 gram portion of each.

       Each weighed portion was then placed in a 30 m.L teflon cup to which was

       added nitric acid, hydrofluoric acid and perchloric acid.             The teflon

       cups were then heated on a hotplate at ca. 120*C, each cup remaining on

       the hotolate until the sample had been totally digested, acid was added

       to each cup as needed until digestion was completed. once the sample

       was digested, heating was continued until the sample volume was reduced

       to approximately 1 mL to which 2.5% nitric acid was added to bring the


                                                 8








      sample volume up to 25 mL.        Samples were then analyzed with a

      Perkin-Elmer 3030-B atomic absorption spectrophotometer (AA) using a

      flame furnace for Al, Fe and Zn and a graphite furnace for As, Ba, Cd,

      Cr, Cu and Pb. A Perkin-Elmer 460 AA equipped with cold vapor apparatus

      was used for analyses of samples for Hg.



           The mean values of the analyses of replicate samples were utilized

      as data for statistical comparisons. Statistical procedures employed in

      this study are detailed in Sokal and Rohlf (1969) and Fi'lliben (1975).



           Quality of analytical technique was assured through particpation in

      the intercomparison exercise for sediment metal analyses (FDER, 1991).

      This exercise involved the digestion and analyses of standard reference

      sediments from the National Institute of Standards and Technology (NIST

      SRM 1646) and the National Research Council of Canada (NRC BCSS-l and

      BEST-1). Coastal sediments of a variety of types were also incorporated

      in the intercomparison exercise. Analytical results-obtained by the

      ADEM Mobile Branch Laboratory were compared to those of other labs

      participating in the exercise. These results indicate a high degree of

      reliability in the analytical data produced by the ADEM lab.           In

      addition to participation in      the intercalibration exercise, ADEM

      laboratory personnel routinely checked performance of their digestion

      technique and analytical instruments by testing samples of reference

      material during the course of this study.









                                            9
















                                                                        TE- 1

                                                             RR- I     RR-2
                                                              LCC     TE-2

                                                          SR_
                                                                 AR-     BM- 1
                                                      MD- 1.@@ ;*- TE-   BR-1
                                                              MD-2

                                               DR- I           MB-7


                                                                MB-6


                                              TI
                                                       TI-2             FB- 1


                                                                       PC- 1
                                                       *FRP    *MB-5
                                                         MOBILE                   FR- 1
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                                                                       MP-2*    lw B--
                                                      *Pi-l                                      wc- 1.@

                                                              MB-4                                         ic
                         MISSISSIPPI     MS-1                                CP-l                  WB-1
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                                                                             MB-3          --- SP-1
                                           MB-                                                       IV
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                                   MEXICO           S I - ll@o FM-1                   10                 0






                                                   Table 1



                                            STATION LOCATIONS
                                          LATITUDE - LONGITUDE


              STATION                        NORTH LATITUDE                   WEST LONGITUDE


               MB-1                                30*15.88'                        88*10.45'
               MB-3                                30*18.26'                        88*51.01'
               MB-4                                30*20.88'                        67*59-53'
               MB-5                                30*26-52'                        87*59-16'
               MB-6                                30'32.29'                        87'59.04'
               MB-7                                30*36.80'                        87*59.00'
               SR-1                                30*42.46'                        88*42.46'
               RR-l                                30*45.79'                        87*58.69'
               RR-2                                30'46.15'                        87'56.82'
               LCC-l                               30*43.92'                        87*58.78'
               TR-1                                30*46-98'                        87*56.47'
               TR-2                                30*43.90'                        87*58.28'
               TR-3                                30'40.49'                        88*00-40'
               MD-1                                30*39.20'                        88*02.75'
               MD-2                                30*38.52'                        88*02-66'
               DR-1                                30*36.38'                        88*06.55'
               HI-1                                30*31.40'                        88*03.20'
               PC-l                                30*29.10'                        87*56.19'
               FE-1                                30*31.62'                        87*54.66'
               DB-1                                30*35.79'                        87*55.63'
               BR-1                                30*40.501                        87*55.43'
               BM-l                                30*41.69'                        87*55.34'
               AR-1                                30*41.09'                        87*56.09'
               MP-1                                30'26.35'                        87*56-65'
               MP-2                                30'23.59'                        87*54.01
               WKB-l1                              30*23.80'                        87'49.72'
               FR-1                                30'23.72'                        87*49.36'
               CP-l                                30*20.04'                        87'48.97'
                                                   30*31.74'                        88*08.50'
               TI-2                                30'31.77'                        88*07.14'
               FRP-l                               30'27.60'                        88*04.12'
               pi-i                                30*22.74'                        88*06.04'
               MS-1                                30'17.10'                        88'13.26'
               MS-2                                30*13-62'                        88*18-37'
               E-1                                 30'r-1.70'                       88*24.92'
               icww                                30o16.54'                        87*45-15'
               OB-SW                               30'15.75'                        87*44.36'
               BWR-1                               30'29.00'                        87*26-45'
               PR-1                                30'27.23'                        87'25.03'
               PR-2                                30*26.83'                        87*23.60'
               GP-1                                30-24.90'                        87*24.031
               PB-l                                30*24.45'                        87*29.84'
               PB-2                                30*25.56'                        87*22-58'
               PB-3                                30*19.84'                        87*30.00'
               SP-1                                .30'17.78'                       87'34.65'
               WC-1                                30*20.721                        87'36.09'
               ICWE                                30'17.93'                        87*32.46'
               BP-l                                30*18.32'                        87*30.93'
               BSJ-1L                              30'17.57'                        87*31.43'
               AP-1                                30`6.45'                         87*33-23'
                                                       'L
               si-i                                30'12.10'                        88'05.10'
               FM-1                                3r,"13.20'                       87*59-60'










                                       RESULTS



           Application of the concept of utilizing aluminum as a reference

      element in conjunction with parametric statistical analyses demands that

      the data for metals have constant variance and a normal distribution.

      The test for constant variance was performed by constructing plots of

      sample means versus sample standard deviations for each metal. Standard

      deviations were proportional to mean values for all metals. Mean values

      for metals were then converted to log-10 values and plotted against

      standard deviations.     The proportionality between mean values and

      standard deviations was removed indicating the presence of constant

      variance in the data set.




           Presence of normal distribution was determined by calculating

      normal scores for a sample size of N=53 and plotting them against the

      data for sediment metals concentration.     The presence of a relatively

      linear plot indicating a normal distribution.        This procedure was

      performed for both absolute concentrations and for log-10 transformed

      values. Some elements, aluminum, chromium and iron, appeared to fit a

      normal distribution using      absolute concentrations whereas others,

      arsenic and cadmium, required a log-10 transformation to conform to a

      normal distribution. The remaining elements, barium, copper, lead,

      mercury and zinc, failed this graphical test for normal distributions

      regardless of using untransformed or transformed data.           Graphical

      representation of these results are shown in Appendix A.      Presence of

      normal distributions was tested in a more rigorous manner using the

      probability plot coefficient test       (Filliben, 1975).    obtaining a

      significantly high correlation coefficient between normal scores and


                                            12









      metals data leads to the acceptance of the null hypothesis (Ho) of

      normality and the rejection of the alternative hypothesis (Ha) of

      non-normality, results of this test are shown in Table 2. Untransformed

      arsenic, barium, cadmium, copper, mercury, lead and zinc deviated from

      normality.    Untransformed aluminum, chromium and iron values fit a

      normal distribution. Log-10 transformed arsenic, cadmium and zinc data

      produced normal distributions but transformed data for barium, copper

      and lead yielded coefficients just short of the critical value. Both

      untransformed and log-10 transformed data for mercury failed to conform

      to a normal distribution.




           The untransformed values for        aluminum were utilized as the

      independent variable for all comparisons in this study. Untransformed

      values for chromium and iron served as dependent variables for those

      elements; log-10 transformed data were utilized as the dependent

      variable sets for arsenic and cadmium.     As mentioned above the data for


      barium, copper, lead and zinc did not exhibit a normal distribution;

      however, when samples that were suspected of being enriched were removed

      .rom the data set these elements also exhibited a normal distribution.


      Once again, mercury failed to conform to a normal distribution even as a

      11 trimmed" set of data.   A discussion of "trimming" the data set and

      analyses of data from "clean" sites follows later in this section.



           Having examined the data for normality and constant variance the

      next step was to determine the strength of metal/aluminum     relationships.

      Correlation coefficients were calculated for each metal and aluminum,

      these are listed in Table 3. Concentrations of all metals except



                                             13









       mercury   were positively     correlated with     aluminum concentrations

       (p<0.005). Iron and chromium displayed the strongest relationships with

       aluminum; cadmium     the weakest.     Mercury showed a      weak inverse

       correlation with aluminum and consequently was not referenced to

       aluminum values. Schropp and Windom (1988) found a similar inverse

       relationship between mercury and aluminum and also refrained from

       comparing mercury values to aluminum values.



            The next step was to analyze the data for associations between the

       independent variable, aluminum, and dependent variables, other metals.

       Least squares regression analysis was used to evaluate the relationship

       between the metal concentrations and aluminum concentrations. Results


       of the regression analyses are presented in Table 4.



            The results of the regression analyses were then utilized to

       calculate 915% prediction 'Limits according to the procedure of Sokal and

       Rohlf (1969). Regression lines and prediction limits for each metal are

       plotted in.Appendix B, superimposed on the metal vs aluminum graphs.



            The analytical result of each metal was then plotted against its

       respective aluminum value.      These   are graphically represented in

       Appendix B. Superimposed on the graphs are the regression lines and 95%

       prediction bands for each metal/aluminum relationship.       These results

       indicate a proportional relationship between the concentration of

       aluminum and the other metals except for mercury. Data for all metals

       is presented in tabular form in Table 5.





                                             14










                                            Table 2




                          Probability plot correlation coefficients
                                for normallty of metals data.


                                     Correlation Coefficient


                       Metal            Untransformed        LOG 10-Transformed



                   Aluminum                 0.964               0.890


                   Arsenic                  0.851               0.982


                   Barium                   0.942               0.936


                   Cadmium                  0.858               0.976


                   %Chromium                0.974               0.913

                   Copper                   0.912               0.949

                   Iron                     0.966               0.882


                   Me-rcury                 0.837               0.897

                   Lead                     0.863               0.943

                   Zinc                     0.788               0.962



                      p>0.0055 (Accept Ho; normal    distribution)
                      p<0.005 (Reject Ho; non-normal distribution)



















                                                 15











                                       Table 3





                              CORRELATION COEFFICIENTS FOR
                                  METALS AND ALUMINUM


                       Metal                                   r



                    Arsenic                                  0.84*


                    Barium                                   0.68*


                    Cadmium                                  0.64*


                    Chromium                                 0.96*


                    Copper                                   0.83*

                    Iron                                     0.98*


                    Mercury                                 -0.13

                    Lead                                     0.84*


                    Zinc                                     0.86*



                       p< 0.005



























                                              16











                                            Table 4



                     Results of regression analyses using aluminum as
                       the independent variable and other metals as
                                        dependent variable.

                        Metal                 a                      b



                     Arsenic              0.14361943             0.00001621


                     Barium               23-9307788             0.00337917


                     Cadmium              -0.6197267             0.00000597


                     Chromium             6.34129908             0.00104977


                     Copper               0.476601-19            0.00001151

                     Iron                 544-383827             0.52196488

                     Mercury              -0-1700004             -0.0000008

                     Lead                 0.46022156             0.00001311


                     Zinc                 1.11002323             0.00001363



                     a = Y-intercept of regression line.
                     b = Slope of regression line.

























                                                  17







                                                                                             Table 5


                                                                            Sediment Metals Data


                     STATION           Aluminum        Arsenic      Barium          Cadmium     C'  iromium     Copper          Ir  on        Mercury        Lead           Zinc

                     ---------------------------------------------------------------------------------------------------------------

                     MB-1                68,300           24.0         281.5          0.910           82.0         12.50        42,000          0.400         25.00          105.5
                     VIB-3               96,900           82.5         251.5          0.560           90.0         25.20        53,400          0.520         22.95          139.0
                     MB-4                93,850           62.5         222.5          0.490           87.5         23.50        45,600          0.835         22.65          142.0
                     MB-5                911,600          70*5         209*0          0,590           91,0         21*25        50,1110         0,610         22*75          173,1
                     MB-6                76,650           46.5         249.5          0.575           75.5         17.60        42,000          0.400         211.15         126.5
                     MB-7                64,950           34.5         250.0          0.575           68.0         15.05        33,050          0.400         17.95          105.5
                     RR-1                62,750           33.5         242.0          0.485           69.0         15.85        30,100          0.750         15.45            93.5
                     RR-2                75,000           46.0         313.5          0.550           77.5         20.30        35,950          0.450         18.15            94.0
                     SR-1                71,400           41.0         251.0          0.495           67.5         15.90        40,250          0.560         13.40            88.5
                     TR-1                65,450           40.5         366.5          0.540           68.0         19.70        32,1150         0.400         17.90          141.5
                     TR-2                45,900           34.5         199.0          0.495           45.5         11.60        20,550          0.400         12.05            60.5
                     TR-3                34,650           21.0         118.0          0.515           48.5          8.50        19,300          0.400           8.00           68.5
                     LCC-1               78,650           19.0         346.0          0.790          112.5         21.50        40,950          0.400         16.00          180.0
                     AR-1                16,900             5,3        727*0          0,750           51-5         10*00        26,1150         0,400         21*50            79,5

                     BM-1                46,250           1-2.0          27.0         0.510           40.0         11.50        24,200          0.400         19.50            94.0
                     BR-1                36,850           23.0           33.5         0.685           40.0          8.00        27,050          0.400         21.50            56.0
                     MD-1                88,400           106.0        263.5          1.150          107.5         27.50        46,450          0.400         34.00          202.0
                     MD-2                82j550           71.0         258.5          0.720           93.5         21.00        47,750          0.400         20.50          143.5
                     HI-1                67,000             5.5        217.5          0.615           80.0         30.50        34,150          0.400         15.50            94.0
                     DR-1                75,450           11.0         257.5          2.050          111.0         66.00        37,750          0.400         100.00         206.0
                     DB-1                53,400           23.5           30.0         0.580           55.0         i2.00        30,800          0.400         18.50            84.0
                     FB-1                 2,310             3.0          28.5         0.445            8.0          i.50         1,700          0.400           4.00             9.5
                     PC-1                 5,220             3.0          17.5         0.385           17.0          1.75         3,185          0.400           5.00           .0.0
                     ICW-W                5,155             2*0           4*0         0,505           12*0          1,10         1,800          0,4011          3*00             8,0

                     OB-1                37,200             9,5           4.5         0.500           54.0          7.00        23,1100         om4oo         13.00            51.5

                     WB-S                74,350           14.0           15.5         0.810           89.5         II.Co        30,2550         0.40C         27.00            82.5
                     ICW-E               11,101             6*5          22,0         0*291            3*6          3,85             148        0,400           2,50           18,5
                     PB-1                78,450           19.5         250.0          1.460          100.0         12.50        48,230          0.550         25.50          111.0

                     BP-l                 3,300             2.0           9.0         0.245            2.9          0.90             219        0.400           1.50           11.0

                     AP-1                 1,100             2.0           8.0         0.285            4.2          0.90             314        0.400           2.00           17.15

                     E-1                  3,350             2.0          23.5         0.470           11.5          2.00         1,260          0.400           3.50             7-1
                     Cp-1                 9,800             1.5          84.0         0.300           19.0          3.95         8,190          0.950           6.65           21.0

                     FR-1                71,750             6.8        .53.0          0.400           87.5         24.00        36,850          0.950         37.50          119.0

                     MP-1                86,700             8.0        464.5          0.400          100.0         25.00        44,900          0.900         29.00          136.0
                     MP-2                43,500             5.8        250.C          0.300           62.0         15.50        26,850          0.950         23.50            71.5

                     VAB-1               61,000             6.4        320.5          0.450           76.0         20.50        34,900          0.900         32.00            90.5
                     11"-1               62,850             6,8        175,0          11,150          60,5         22,00        31,550          0,900         35*50            56,C

                     PR-1                58,050             4.8        193.0          2.250           62.0         18.50        26,600          0.950         33.50            77.0
                     TI-1                43,150             4.8        290.0          1.500           65.5         27.00        28,700          2.550         30.00          847.5
                     TI-2                66,050             4.9        400.0          0.400           88.5         19.00        33,400          1.250         26.00            92.0
                     FRP - 1             73,500             7.1        389.5          0.450          104.0         24.00        42,850          1.350         29.50          175.C
                     pi-I                 8,700             1.4          63.0         0.250           1-6.0         2.80         5,845          1.250           5.50           16.0
                     MS-1                20o85O             3.4          68.0         0.300           31.0          5.40        13,550          1.000         10.00            37.5
                     MS-2                 1,021             0.9           4.7         0.300            7.0          1.10             917        1.000           2.00             7.0

                     BSJ-1                    373           0.9           8.0         0.170            7.0          6.50             159        0.900           0.90           13.0
                     Gp-1                29,100             2.0        163.5          0.240           38.5         15.00        15,900          0.900         14.70            52.5
                     PB-2                38,500             2.9        193.0          0.250           52.0         17.50        22,600          0.900         20.05            70.5
                     PB-3                 1,365             0.9           7.5         0.090            8.0          7.00             659        0.900           3.20           31.5
                     PR-2                36,250             2.9        203.0          0.395           49.5         19.50        19,600          0.900         19.90            67.5
                     SP-1                 1,855             0.9           8.5         0.215           10.5          8.00             925        0.900           1.50           14.5
                     WC-1                29,400             2.5          95.0         0.175           40.5         13.50         9,270          0.900           8.85           39.5
                     SI-1                     857           0.9          12.5         0.090            1.9          3.80             774        0.900           0.65             3.2

                     F4-1                     730           0.9          15.5         0.090            2.0          4.45             712        0.900           0.95             4.6


                                                                                                         18









            So far this exercise has demonstrated statistically significant

       relationships between     aluminum and the metals        arsenic, cadmium,

       chromium, iron and zinc. The metals barium, copper and lead did not fit

       a normal distribution but appeared to be somewhat skewed to the left

       indicating a data set enriched in these elements. Since the primary

       objective of selecting sample sites was the sampling of a broad spectrum

       of sediment types rather than selecting only those sites far removed

       from sources of potential contamination, there was the chance that some

       samples were enriched due to anthropogenic activity. The next part of

       the discussion deals with examination of a "clean" set of data.




            As stated above, the intent of choosing the locations was directed

       more towards thouough coverage of the coastal area and a wide variety of

       sediment types rather than avoiding potentially contaminated areas. The

       observed lack of normality in the data for barium, copper and lead,

       combined with the potential for enrichment of the sediments of western

       Mobile Bay from urban non-point sources, the extensive industrial

       activity in the Mobile area and from the sources discussed in the

       introduction led to deleting from the data set those samples from the

       western half of Mobile Bay including the tributaries.              Additional

       rationale for this action was provided by analyses of sample material

       from a ditch draining a bauxite tailings impoundment at the old ALCOA

       facility.   This material was a fine grained "mud" typical of the

       contents of the impoundment. These results indicate that the material

       collected from the ditch was indeed enriched with aluminum far above

       that of any sample of natural sediment collected during this study.

       The nature and quantity of bauxite mud in the ditch together with the



                                              19









      direction of drainage (towards the Mobile River) appears to indicate

      that the tailings impoundments have been a likely source of metals

      enrichment to Mobile Bay.



           Subsequent analyses were performed on this set of data, samplesize

      N=38, referred to hereinafter as the "clean" data set.



           Statistical analysis of the "clean" data set was handled the same

      as for the entire data set. Graphical plots of normal scores versus

      concentration values    were constructed    and the     probability plot

      coefficient test was applied. The results of these proceedures indicate

      a normal distribution for the untransformed values of barium, chromium,

      copper, iron, lead and zinc, and for the log-10 transformed values of

      arsenic and cadmium. Graphical representation of these plots may be

      found in Appendix C and probability plot correlation coefficients in

      Table 6. The presence of homoscedasticity was tested by the same method

      as discussed earlier.




           After determining that     the "clean" set of      data meets the

      requirements of parametric statistical analyses, the "clean" set was

      subjected to least squares regression analyses (Sokal and Rohlf, 1969).

      The results of which are presented in Table 7, correlation coefficients,

      and Table 8, regression equations. The correlation coefficients for the

      "clean" data set show a relationship between aluminum and metals

      approximately the same as those for the entire data set.          Although

      11 trimming" the  data may not have      strengthed the metal/aluminum

      relationships of the "clean" data set, it did result in normal



                                            20








      distributions for    barium, copper    and lead,    indicating possible

      enrichment for these elements in sediments of western Mobile Bay.



           The results of regression analyses were then utilized to calculate

      95% prediction limits as with the entire data set. The graphical plots

      of metals vs aluminum complete with regression lines and 95% prediction

      limits for the clean data set are presented in Appendix D. As the reader

      will observe the width of the prediction limits vary among the different

      elements. This is a function of the correlation coefficents for the

      metal to aluminum relationships, as the magnitude of the correlation

      coefficents increase the width of the prediction limits decrease.



































                                           21











                                         Table 6




                        Probability plot correlation coefficients
                        for normality of clean sites metals data.



                                  Correlation Coefficient


                     Metal            Untransformed       LOG 10-Transformed



                 Aluminum                0.955                0.919


                 Arsenic                 0.868                0.978


                 Barium                  0.963                0.903


                 Cadmium                 0.837                0.978


                 Ch--omium               0.971                0.943

                 Copper                  0.977   *            0.948

                 Iron                    0.957   *            0.913


                 Mercury                 0.861                0.853

                 Lead                    0.968                0.949


                 Zinc                    0.967                0.959



                    p > 0.01 (Accept Ho; normal distribution)
                    p < 0.01 (Reject Ho; non-normal distribution)



















                                                 22










                                      Table 7





                             CORRELATION COEFFICIENTS FOR
                                 METALS AND ALUMINUM
                                 "CLEAN SITES" DATA



                      Metal                                    r



                   Arsenic                                     0.81 *


                   Barium                                      0.69 *


                   Cadmium                                     0.66 *


                   Chromium                                    0.97 *

                   Copper                                      0.81 *

                   Iron                                        0.97 *

                   Mercury                                    -0.09

                   Lead                                        0.87 *


                   Zinc                                        0.93 *



                     P < 0.005

























                                               23










                                        Table 8




                      Results of regression analyses of data from
                    "clean sites" using Aluminum as the independent
                  variable and other metals as dependent variables.

                     Metal                a                    b



                  Arsenic               0.172176             0.000015


                  Barium                4.259297             0.004070


                  Cadmium               -0.652876            0.000007


                  Chromium              4.335524             0.001102

                  Copper                0.449245             0.000012

                  Iron                 395.383860            0.519763


                  Mercury               -0.194462            -0.000001

                  Lead                  0.388669             0.000016


                  Zinc                  1.049655             0.000015



                  a = Y-intercept of regression line.
                  b = Slope of regression line.

























                                              24











                                     DISCUSSION



            Application of the results of this study to monitoring efforts is

       fairly straightforward. The regression line and prediction limits of a

       specific metal to aluminum relationship from the "clean" set of data are

       reproduced on a graph either by hand or by means of computer graphics

       so'Ltwa--e. Then the value of a meta    1 at a station is determined


       (utiliztion of mean values calculated from replicate or triplicate

       samples from    each station    is strongly recommended)      and points

       representing the corresponding metal to aluminum values are plotted on

       the graph. If a point falls within the prediction limits then the metal

       is within the natural limits.       If a point lies above the upper

       prediction limit then the sample is considered enriched in that specific

       metal. The greater the distance above the upper prediction limit, the

       greater the chance that the sample is from an enriched area and the

       greater the degree of enrichment of that sample.



           An example of this procedure is as follows. During our sampling we

       collected sediments from Dog River a tributary of Mobile Bay, this site

       is referenced to as station DR-1 in the data table and on the map. This

       stream as located in a extensively developed watershed and receives a

       considerable amount of stormwater runoff from paved roads, parking lots

       and other urban non-point sources.     The site where sample DR-1 was

       collected is also a popular recreational area with a high density of

       boat traffic. Consequently this location has been subjected to years of

       exposure   from emissions    from boat    motors and     motor vehicles.

       Consultation of the data in Table 2 reveals this site to also be the one


       with the highest lead concentration of all sites sampled.


                                            25










            With this in mind site DR-1 was deleted from the clean data set and


       was chosen as a test case for evaluation of possible enrichment with

       lead. The value for lead at this location was then plotted on a graph

       of the lead/aluminum relationship.     This example is illustrated in

       Figure 2 and shows the lead concentration to be well above the upper

       prediction limit. From this, it is reasonably certain to conclude that

       the sediments at this site are enriched with lead.       This information


       along with knowledge of the geology and land use practices of the

       drainage basin would appear to indicate that exhaust emissions from

       internal combustion engines are the likely source of enrichment. Of

       course this preliminary assessment should be followed up with a more

       extensive survey of sediments in the river basin.



           Although this method appears to be a useful tool for identifying

       areas of enriched sediments the author offers the following caveat so

       as to minimize the chance of misinterpretation of data. Points lying on

       or just above the upper prediction limit should be evaluated with

       caution. Such judgements are best made when assisted by analyses of

       samples from nearby stations and ancillary data such as proximity and

       nature of wastewater discharges and/or non-point sources.       Also, the

       necesscity for utilizing the mean value of the analyses of duplicate or

       triplicate samples cannot be emphasied too strongly.       Widely varying

       results for replicate samples from a station may be an indication of

       errors in the digestion and analytical procedures.      Additionally, an

       effective laboratory Q&A program is invaluable for obtaining reliable

       results and if possible should incorporate certified reference sediments

       such as those available from the National Institute of Standards and


       Technology.

                                            26







                                  SEDIMENT LEAD CONCENTRATION

                                                       STATION DR-1
                   150


                   140




                   120


                   110

            nL     100                                                               0
                                                                                                              rt
            z
            0
                                                                                                              (D




                                                                                                              rt
            w       70
            Q                                                                                                 rt
            z       60                                                                                        0)
            0                                                                                                 (t
                    50                                                                                        0


                    40


                    30


                    20


                    1 G




                        0              20               40              60              so              100
                                                            (Thousands)
                                               ALUMINUM CONCENTRATION (ppm)










                                     CONCLUSION



           The results of this study appear to have established the existence

      of statistically significant relationships between aluminum and eight of

      the nine metals analyzed in "clean" sediments from Alabama estuaries.

      The relationships are defined by the regression lines for each metal vs

      aluminum, estimates of the ranges of values to be expected from samples

      of clean sediments in Alabama are given by the prediction limits. The

      regression lines and prediction limits of the "clean" data set can be

      used to identify unnatural concentrations of metals in sediments from

      Alabama estuaries.




           This technique will be applied in the near future to a survey of

      shipyards in coastal Alabama. The objective of this study will be the

      evaluation of metals enrichment of sediments in and around shipbuilding

      facilities. These results are to be reported in a forthcoming document.



























                                           28












                                      REFERENCES



      Filliben, J.J. 1975. The probability plot correletion coefficient test
           for normality. Technometrics 17: 111-117.

      Duce, R.A.; G.L. Hoffman; B.J. Ray; I.S. Fletcher; P.R. Walsh; E.J.
           Hoffman; J.M. Miller; J.L. Heffter; G.T. Wallace; J.L. Fasching
           and S.R. Pitrowicz. 1976. In: Marine Pollutant Transfer, Heath and
           Co., Lexington, MA. p 77.

      Florida Department of Environmental Regulation, Coastal Zone Management
           Section. 1991. Results of intercalibration exercise for sediment
           metal analyses, draft report. FDER, Tallahassee, FL. 19 pp.

      Goldberg, E.D., J.J. Griffin, V. Hodge, M. Kolde, and H. Windom. 1979.
           Pollution history of the Savannah River estuary. Environmental
           Science and Technology. 13: 588-594.

      Isphording, W.C., and G.M. Lamb. 1985. Sedimentation, dispersal and
           partitioning of trace metals in coastal Mississippi-Alabama
           estuarine sediments. Mississippi-Alabama Sea Grant Consortium
           Project No. R/ER-4. 29 pp.

      Isphording. W.C., and G.C. Flowers. 1987. Mobile Bay: The right
           estuary in the wrong place. In T.A. Lowery (ed.), Symposium on
           the natural resources of the Mobile Bay estuary. Alabama Sea Grant
           Extension Service. Sea Grant Publication No. 87-007

      Malatino, A.M. 1980. Chemical quality of bottom sediment samples from
           Mobile Bay, Alabama. Geological Survey of Alabama. GSA Contract
           No. 80-3052. 23 pp.

      Schropp, S.J. and H.L. Windom. 1988. A guide to the interpretation of
           metal concentrations in estuarine sediments. Florida Department of
           Environmental Regulation, Tallahassee, Florida. 44 pp w/ appendix.

      Sokal, R.R. and F.J. Rohlf. 1969. Biometry: the principles and
           practice of ststistics in biological research. W.H. Freeman and
           Company, San Francisco. 776 pp.

      Taylor, S.R. 1964. Abundance of chemical elements in the continental
           crust: a new table. Geochem. Cosmochem. Acta 28: 1273-1286.


      Trefey, J.H.; S. Metz and R.P. Trocene. 1985. The decline in lead
           transport by the Mississippi River. Science 230: 439-441.

      Turekian, K.K.; K.H. Wedepohl. 1961. Geol. Soc. Am. Bull. 72: 175-192.

      Windom, H.L.; R.G. Smith and C. Rawlinson. 1989. Particulate trace
           metal composition and flux across the Southeastern U.S. Continental
           Shelf. Marine Chemistry, 27: 283-297.



                                           29











      Windom, H.L.; S.J. Schropp; F.D. Calder; J.D. Ryan; R.G. Smith; L.C.
           Burney; P.G. Lewis and C.H. Rawlinson. 1989. Natural trace
           metal concentrations in coastal marine sediments of the
           Southeastern United States. Environmental Science and Technology
           23: 314-320.





























































                                          30


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                               NORMAL SCORE VS ALUMINUM VALUE

                   2.5



                     2





                                                                                            0
                                                                                  H col
                                                                          oa
                                                    CAP
                                         0







                 -1.5 _0



                   -2 -



                 -2.5           F-                              -T-
                                       20               40               6c.             80
                                                            (Thousonds)
                                                -"%LUMlNUt%,i GONCENTATION (ppm)







                               NORMAL SCORE VS ARSENIC VALUE

                   2.5



                     2


                                                                                     0
                    1.5








                   Q.5

                                                               0

                     0



                  -0.5
                                                00



                                     0


                                     0


                  -2-5
                     -0.6       -0.2       0.2      'D. 6       1        1.4       1.8       2.2       2.6

                                               ARSENIC CONCENTRAMON (LOG)







                                   NORMAL SCORE va BARIUM VALUE


                    2.5 -



                    2.0 -
                                                                                                    0

                                                                                                    0
                    1.5



                    1.0 -



                    0.5



                    0.0
                                                                                   0 dDt:l
                                                                               0
                                                                           EP

                                                              EP

                                                       0






                                           0


                                         0


                  -2.5 -

                                                           1          2          2           2

                                                  BARIUM CONCENTRATION (LOG)








                                  NORMAL SCORE vs CADMIUM VALUE


                     2.5 -



                     2.0 -



                     1.5 -



                     1.0


             Lli
             L       0.5
             0
             cl


                     0.0













                                              0

                                              0






                                                                    -0.5              -0.1      0.1

                                                    CADMIUK-i CONCENTRATION (LOG)







                                NORMAL SCORE vs CHROMIUM VALUE


                    2.5 -

                                                                                             0

                    2. G -
                                                                                             0

                                                                                             0
                    1.5 -








                    0.5


                    G. Q -                                                        da


                                                                           0
                                                           0CY   EP

                                           0
                                        0








                                                                1.2-          1.6          .21.0        2.4
                          0          G.4           0.8

                                                  CHROMIUM CONCE11TRATION (LOG)








                               NORMAL SCORE vs COPPER VALUE


                  2.5 -

                                                                                           0

                  2.0 -



                  1.5 -                                                0



                  1.0



                  0.5



                  0.0


                                             0
                 -0.5
                 -1.0                  C3

                 -1.5



                 -2.0



                 -2.5

                      0.5       0.7        0.9       1.1        1.3       1.5        1.7       1.9

                                              COPPER C-ONCENTR4TION (LOG)







                                     NORMAL SCORE va IRON VALUE


                    2-5 -



                    2.0 -



                    1.5 -



                    1.0 -



                    0.5



                    0. Q -
                                                                                             91
                                                                                   0    0
                                                      0                  0       0

                                              0





                  -2.0





                        2.2          2.6          3.0          3.4           3.8          4.2          4.6

                                                    IRON CONCEKTRA-1-10N (LOG)








                                      NORMAL SCORE vs LEAD VALUE


                    2.5 -



                    2.0 -


                                                                                    0
                    1.5 -








                    0.5



                    0.0



                    -0.5
                                                             EP 0


                                              0
                                              0
                                         F






                   -2.5 -
                       -0.6       -0.2        0.2        ID. 6      1.0        1.4        1.8        2.2        2.6

                                                     LEZ-0 CONCENTRATION (LOG)







                                        NORMAL SCORE vs ZINC VALUE




                     2. Q -

















             M
             L
             0                                                          0 c!P
             z                                                     0



                                                      0
                                                    0
                                                    D


                   -2.0

                                         0

                   -2.5

                         0.0           4          0.8         J.-I        1.6         -1.0        2.4          2.8

                                                       ZINC CONCENTRATION (LOG)





COASTAL PROGRAM

SEDIMENT CHEMISTRY

BASELINE STUDY

APPENDIX B

METAL VALUES

VS

ALUMINUM VALUES








                                          LOG ARSENIC                  ALUMINUM


                    2.6 -


                    2.4 -


                    2.2 -


                    2. 0


            z       1.8 -
            0       1.6                                                           0    0  0
                                                                 0               0
            cr
                    1.4                                  0
            z
                                                                                             0

            77
            0

                    G                                                           0      00
                                                               0
                                                                           0      00


            (-9     Cy 4
            0            cl 0 0
            -i
                                                                                                           0





























                                          20               40                60               80               100
                                                                (Thousands)
                                                  ALUMINUM CONGENFMATION (ppm)







                                                                   BARIUM                    ALUMINUM





                           7CjCj











                 F



                 z         400
                 LLJ

                 z
                 0
                 0

                 7:



                 -3'
                           200                                                  00                         0



                           100


                                                                                            0        0
                               0 --J

                                   0                       20                       40                       60                       80                      100
                                                                                          (Thousands)
                                                                       ALUMINUM CONCENTRATION (ppm)







                                     LOG CADMIUM                 ALUMINUM






                  0 .4-                                             0

                   0.2                                   0
           z


                                                                                 0
                  -0.2                                           0                MO
                                                  00                      in
           LLJ                                                                 0                 0
           0            EP                                                                 0
           z      G. 4



                        0
           :D







                  -1.2


                  -1.4




                                      20              40             60              80              100
                                                          (Thousands)
                                             ALUMINUM CONCENTRATION (ppm)







                                      CHROMIUM            ALUMINUM



                 140 -


                  1301 -



                                                                               0

                                                                           0
           z
           0
           F@
           tk
                                                                          0


           w                                                                  cl
           0
           z      70 -                                                    0
           0
                  60
           :D     50                                    0

           0
           LL     4 G -                                0
           T
                  30


                  20        0





                                   20             40             60             80            100
                                                      (Thousands)
                                          ALUMINUM CONGENTRAMON








                                         LOG COPPER                  ALUMINUM


                    2.6 -


                    2.4 -


                    2.2 -


                    'D. 0 -


                    1.8


                    1.6
                                                                                               ---OEI
             0      1.4
             F-:
                                                                                              El
                                                       00

             F-
             7                                                       E3


             z
             0
             0
             L      0. c-
             LLJ
             Li     ID. 4
             r,
             0
                    0.2   0  0




                   -0.2


                   -0.4


                   -0.6

                         0               20               40               60              80               100
                                                              (Thousands)
                                                ALUN41NUM GONCENTRATON (ppm)








                                                 IRON         ALUMINUM

                     60






                     .50

                                                                                                   0     0


                     40



            0



                     30

                                                                 0        13



                                                                0
                     20












                         0               "0               40                60               80              100
                                                               (Thousands)
                                                 ALUMINUM CONCE1,4TRATION (ppm)







                                            LOG LEAD              ALUMINUM


                    2.6 -


                    2.4 -


                    2.2 -


                    2.0 -


                    1.8

                    1.6                                                              0             0
                                                                                0          0
            z       1.4                                                                                    00
            0                                                         0        11D
                    1.2                          0                            0 0          0
            CL                                                                       0
            z       1.0
            Ld
            U
            z                  0
            0                0
            0       0.6
            ci               0
            -:3     Q . 4


                    0.2


                    0.0





                   -0.4


                  -Q. 6
                        0                2 0              40               60               80               100
                                                              (Thousands)
                                                 ALUMINUt-A CONCENTRATION (ppm)








                                               LOG ZINC             ALUMINUM





                     2.6 -


                     2.4 -


                     2.2 -
                                                                                   0

                     2.0 -

             z
             0
             F@
             zx
                     1.6 -

             z
             Lij     1.4 -
                                  0
                          0
             0       1.2 -
                          P
                     1.0    0
             N       0.8  0

                          F-1
                     0.6
                          0
                     0.4


                     0.2


                     0.0
                          0                20               40                60                80               100
                                                                                          0@0




















                                                                 (Thousands)
                                                   ALUMINUM CONCENTRATION (ppm)




COASTAL PROGRAM

SEDIMENT CHEMISTRY

BASELINE STUDY


APPENDIX C

NORMAL SCORES

VS

METAL VALUES

"CLEAN" DATA








                                           NORMAL SCORE VS ALUMINUM VALUE




                                                                                                                                    0


                                                                                                                           0


                                                                                                                       El
                                                                                                                      0



                 Lli
                 L                                                                                  E]
                 0
                 0
                 69                                                                0

                  I
                 <                                                Ep
                                                         0
                                            CP
                 0
                 z



                                   0
                                   0

                                   r-l

                                -  El






                                                        20                    40                     60                     80                     100
                                                                                    (Thousands)
                                                                  ALUMINUM CONCENTRATION (ppm)







                               NORMAL SCORE VS ARSENIC VALUE

                  3.0



                  22.0                                                         cl


                  1.0 -                                           0

                  0.0 -                                log
                                                       Li








                                    0
                                    0
                                    0
                  -2.0              0




                  -3.0

                     -0.6      -Q.-)      0.2-      Q. 6      1.0       1.4       1.8


                                             LOG-10 ARSENIC CONCENTRA-FION







                                NORMAL SCORE VS BARIUM VALUE




                    2.0






                    1.0




                               nQ













                  -2.0






                  -3.0

                       0                  200                 400                 600                 800

                                               BARIUM CONCENTRATION (ppm)







                                NORMAL SCORE VS CADMIUM VALUE





                                                                                            0

                                                                                    13
                                                                                  11
                                                                                 0
                                                                                0


            Ld
            a@
            0
            0
            69




            (Y
            0





                                          0
                                          0









                      -1.5     -1.3    -1.1    -0.9    -0.7     -0.5    -0.3    -0.1     0.1     0.3     0.5


                                               LOG-1 0 CADMIUM CONCENTRATION







                              NORMAL SCORE VS CHROMIUM VALUE




                    2.0


                    1.0                                               EP   OP
                                                            CF
                                                          ly
                    0.0
                                            0    Off
                              C@y



                        0

                  -2.0






                  -3.0

                       0            20            40            60           80           1 Go          120

                                              CHROMIUM CONGENTRATON (ppm)







                               NORMAL SCORE VS COPPER VALUE


                   3.0 -






                   2.0 -





                                                                             0
                   1.0                                                    ly0

           0
           C)
           U)
                   G. 0                          Ei-LJ

           of
           0
           z






                         0

                  -2.0






                  -3.0
                       0          4         8         12         16        20         24         28

                                               COPPER CONCENTRATION (ppm)







                                      NORMAL SCORE VS IRON VALUE




                    2.0



             LLJ                                                                00
             ft@                                                             hp
             0

                                                                   0
              1                                            o LJ
                                         0
                               cl 0
             0








                          -71










                                                                                              40
                                                                (Thoustind s)
                                                    IRON CONCENTRATION (ppm)







                                 NORMAL SCORE VS LEAD VALUE




                  2.0




                                                                                   0
                                                                             0
                  1.0                                                 00







                         0





                       0





                      0                  10                 20                 30                 40

                                               LEAD CONGENMATION (ppm)







                                   NORMAL SCORE VS ZINC VALUE








                                                            0
                                                      EP

                                              17)













                   -2







                       0       20      40      60      80      100     120     140     160     180     200

                                                 ZINC C0NCEN`rRAT10N (ppm)





COASTAL PROGRAM

SEDIMENT CHEMISTRY

BASELINE STUDY

APPENDIX D

METAL VALUES

VS

ALUMINUM VALUES

"CLEAN DATA"








                                                LOG ARSENIC                      ALUMINUM

                      2. 60 -


                      2.40 -


                      2.20   -


                      2.00   -

              z       1.80
              0
                                                                                             0
              ,jc     1.60                                               0                0
              Q@
              F-      1,40                                                       0
              Ld                                                                                          0
              0       1.20
              z                                                           0
              0
                      1,00

                      0.80                                             0
                                                                          13
              LJ
              V)      0.60
              CL
              <                   0
              C9      0.40
              0
                      0.20

                      0.00  -11 w

                     -0.20


                     -0.40


                     -0.60

                            0                  20                  40                  60                 80                  100
                                                                        (Thousands)
                                                        ALUMINUM CONCENTRATION (ppm)







                                      BARIUM         ALUMINUM



                7GO




                600









                400

                                                                  0






                                                                0

                200
                                                             0
                                                                0



                  QQ

                   G                                0
                                                                      0


                                                 @00


                    G             20            40            60            80           100
                                                   (Thousands)
                                        ALUMINUM CONCENTRATION (ppm)







                                      LOG CADMIUM                 ALUMINUM





                    0.4


                    0.2


           z        0.0
            LLJ                                                                   0
           0      -0.2
                         EP0
                                                                                            0









                        11B


                  -1.2


                  -1.4
                                                                         rE3




















                                       20              40             60                              100
                                                          (Thousands)
                                              ALUMINUM CONCENMATION (ppm)







                                        CHROMIUM             ALUMINUM



                  140 -


                  130  -


                  120  -
            E
            L     1 10 -
            CL

                  100
            0
                                                                              00


            LLJ
            C-1
            7      70
            0
                   60

                   50                                     0

            0
            L      40                                     0
            T
                   30





                   10
                     0         0

                       0             20              40             60              80             100
                                                         (Thousands)
                                             ALUMINUM CONCENTRATION (ppm)







                                          COPPER            ALUMINUM



                   28 -


                   26 -


                   24 -
           E       22 -

                   20 -                                                   0
           z
           0       18

                   16
           z                                 0
           w
                   14 -
           0       12 -                                         0
           0                                              Q3                     0
           IL
           w       10
           CL
           CL
           0        8 -0                           0

                    6


                    4


                    2


                    0

                       0             20              40              60              80             100
                                                         (Thousands)
                                             ALUMINUM CONCENTRATION (ppm)







                                                IRON        ALUMINUM






                    .50 -






                    40 -



            0


                    30






                    20









                     0 T41
                        Q               20               40              60               80              100
                                                             (Thousands)
                                                ALUK41NUM CONCENTRATION (ppm)








                               LEAD     ALUMINUM


             ,50 -








             40 -

                                                       0


        CL
                                                0
                                                 0
        z
        0    30                                                 0

        F-
        z
        w

             20                          0
        0                                    0
        0                                           0    0
        C)                                        0        Cl












                0         20          40         60         80        100
                                        (Thousands)
                                ALUMINUM CONCENTRATION (ppm)







                                                                          ZINC               ALUMINUM

                             2GO



                               BG

                             170

                             1 E>G

                             15G

                             140

                             130

                             120



                             100
                                                                                                                                      0
                               90                                                                                   0
                               so                                                                                                    0
                               70                                                   0
                               60                                                               0
                               50                                         0          0

                               40                                          0

                               30

                               20

                               10

                                  0
                                     0                        20                        40                        60                       so                        100
                                                                                              (Thousands)
                                                                          ALUMINUM CONCENTRATION (ppm)



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