SlideShare a Scribd company logo
1 of 8
Download to read offline
169




       EVALUATION OF DEGREASERS AS BRINE CURING ADDITIVES
                                                                  b
                 EDUARD HERNANDEZ BALADA, WILLIAM N. MARMER', PETER H. COOKE, AND JOHN C. PHILLIPS
                                     U.S. Department of Agriculture, Agricultural Research Service
                                                   Eastern Regional Research Center
                                                     600 EAST MERMAID LANE,
                                                    WYNDMOOR, PA      19038 USA




                         ABSTRACT                                                                RESUMEN

     The length of time needed for brine curing of raw                      El tienipo requerido en la preservacion de pieles
     hides and skins, a minimum of 18 h, is a time-                         crudas por la acción de salmuera, un mInimo de 18
     consuming process. In this paper we initially report                   horas, es un proceso que consume tiempo. En este
     the results of an investigation of the stratigraphic                   trabajo reportamos inicialmente los resultados de
     distribution of sodium chloride and water in fleshed                   una investigaciOn estratigralica de Ia distribución
     hides cured for varying intervals of time. We                          del cloruro de sodio y del agua en pieles previamente
     demonstrated that salt entered the hide mainly from                    descarnadas y tratadas durante diferentes intervalos.
     the flesh side. Water, on the other hand, was                          Hemos demostrado que la sal penetro La piel
     withdrawn from both sides of the hide; the epidermis                   principalmente por el lado de la came. El agua,
     acted as a semipermeable membrane. Three                               diferenternente, fue extrafda a través de ambas
     commercial degreasers as well as a glycolipid                          direcciones en la piel; la epidermis se comporto
     surfactant (sophorolipid) were tested as brine curing                  como una membrana semipermeable. Tres
     additives and their efficiency evaluated according                     desengrasantes comerciales asI como también un
     to the moisture, salt, salt saturation and fat content                 tensoactivo glucolIpido (soforolIpido) fueron
     levels in the brine-cured hide. One of the commercial                  ensayados como aditivos auxiliares para la
     degreasers, when used at 0.5% w/w, significantly                       preservación por sairnuera y su eficacia evaluada de
     removed fat from the hide as well as enhanced the                      acuerdo a los valores determinados por la huinedad,
     uptake of salt. The sophorolipid also was an                           sal, saturación salina, y contenido degrasa en la
     effective degreasing agent, decreasing the fat                         piel preservada por salmuera. Uno de los
     content of the brine-cured hide and, if used in                        desengrasantes, cuarido se utilizó at 0.5% en peso,
     excess, significantly increasing the uptake of salt.                   significativamente deserigrasO la piel asI como
     The data presented here confirmed that the usage of                    aumentó la absorción de la sal. El soforolIpido fue
     an appropriate degreasing agent in the brine is a                      también un efectivo desengrasante, disminuyendo
     suitable option for reducing the turn-around                           el contenido graso de la piel tratada por salmuera y,
     times in raceways and thus creating additional                         SI su ernpleo fuese en exceso, significativamente
     curing capacity.                                                       aumentarfa también la absorción de sal. Los datos
                                                                            aquI presentados confirmaron que el uso de
                                                                            desengrasantes en la salmuera es una opción
                                                                            apropiada para reducir ci tiempo de rotación en los
                                                                            tanques de salazón y asf aunientar la capacidad
                                                                            adicional del proceso de preservación.




a Current address: Department of Chemical Engineering, University of Barcelona, Marti i Frallquès 1, 08028 Barcelona, Spain
 Corresponding author e-mail address: William.Marmer@ars.usda.gov
Mention of trade names or commercial products in this article is solely for the purpose of providing specific information and
does not imply recommendation or endorsement by the U.S. Department of Agriculture.
Manuscript received November Ii, 2008, accepted for publication November 28, 2008.


                                                                                                               JALcA, VOL. 104. 2009
170                                                  BRINE CuRING ADDITIVES



                        INTRODUCTION                                removal efficiency. Finally, the possibility of using SL as
                                                                    brine curing enhancers was investigated.
Curing of raw hides and skins with common salt (sodium
chloride) is the most popular preservation method used
currently. Sprinkling of solid salt on the flesh surface of the                            EXPERIMENTAL.
hide, known as green-salting, is extensively used in warm
countries like India. Conversely, most American and                 Materials
European hide processing facilities typically treat their hides     Two fresh cow hides were purchased from a local abattoir.
in raceways tilled with a highly concentrated solution of           They were soaked in 200% water with 0.15% Boron TS
sodium chloride (brine). The economics of brine curing of           (Rohm & Haas Co.. Spring House. PA) and 0.10% Proxel
hides and skins have been affected recently by increasing           (Chemtan Co. Inc., Exeter, NH) for 2 h and then fleshed.
commodity prices for sodium chloride.' Furthermore, the             Approximately 6 x 10 in (15 x 25 cm) pieces were cut and
large amount of salt needed creates environmental issues            stored at -20 °C. They were thawed at 4 °C just before use.
when it is soaked out, contributing to 40% of the total             Food grade sodium chloride of minimum purity 99.82% (US
dissolved solids generated in the entire process of leather         Salt Corporation, Watkins Glen, NY) was used in the brine
manufacturing.2                                                     preparation. Three commercial degreasing agents marketed
                                                                    to the leather industry and identified as degreasers 1, 2 and 3,
In our previous paper' we developed a mathematical model            as well as the experimental sophorolipid (SL) developed in
that described the diffusion of sodium chloride into the hide       our research facility, were used without further purification.
during the curing process. We concluded that the usage of           All other chemicals were reagent grade and used as
saturated brine as well as a minimum float of 500% yielded          received.
an optimal diffusion rate. We also proved by means of
epifluorescence microscopy that salt diffused into the hide         Stratigraphic Study
mainly from the flesh side, which presents a less compact          Thawed hide was cut into square pieces of approximately 4
structure and greater porosity than the grain and upper            x 4 in (10 x 10 cm) with an average weight of approximately
corium. However, the fatty or adipose tissue present on the        100 g. They were transferred to a Dose drum (PFI 300-34;
flesh side was reported to retard the diffusion of salt into the   Dose 131 Maschinenbau GmbH, Lichtenau, Germany) and
hide.' Thus, a poor fleshing of the hide prior to the cure may     tumbled at 6 rpm in a 500% float of 95 'SAL brine solution
further aggravate this phenomenon.                                 (25.1 g NaCl/lOO (y brine) for varying time intervals, after
                                                                   which they were removed from the drum, hand-squeezed to
The use of degreasing agents in the leather manufacturing          wipe off excess water, split into three layers (flesh, middle
process is quite widespread and they are mainly utilized           and grain), sealed in plastic bags and stored at 4 °C until
during soaking, liming and deliming to decrease the fat            analysis.
content of the wet blue below the norm value.' However,
there is no literature regarding the usage of these degreasers     Degreaser Study
in the cure. If the use of a degreasing agent along with the       Pieces of hides of approximately 100 g were tumbled at 6
brine could accelerate the penetration of salt into the hide,      rpm in a 500% float of initially saturated brine (100 'SAL,
then turn-around times in the raceways would be reduced            26.4 g NaC1/100 g brine) for 16 h. To the test samples, the
and thus additional curing capacity would be created.              required volume of degreasers 1, 2 or 3 was added to the
                                                                   brine held in the drum and tumbled for jive minutes to ensure
Sophorolipds (SL) are glycolipid surfactants produced in           a uniform distribution of the product within the brine. Due
large quantities by the yeast Candida bonbico1a. Among             to its low solubility, the SL solution was prepared in the
their desirable properties, they are biodegradable, non-           laboratory by adding the required amount of SL powder to
ecotox ic, and non-foaming ,6 Sophorol ipids are currently         the saturated brine solution and stirring for at least 24 h, after
used in the cosmetic industry and as an active ingredient of       which the solution was dumped into the drum. An SL
dishwashing detergents. 7 The potential for their use in the       solution that had been filtered through a sintered glass funnel
leather industry as a degreasing agent is therefore worthy of      immediately after 24 h of stirring was also tested. Control
consideration.                                                     samples to which no degreaser was added were also run for
                                                                   all experiments. The concentration of degreasers or SL was
In the present paper we first carried out a stratigraphic study    always expressed with respect to the combined weight of
to monitor the distribution of sodium chloride and water in a      hide and brine. No further salt or brine was added to the
hide throughout the curing process. The effect of the cure on      drums during the experiments. Brine density was determined
the collagen denaturation temperature was also examined.           by gravimetric analysis. Hide density was assumed to be Ig!
Furthermore, we used scanning electron microscopy in               cm3.
backscattering electron mode to establish changes in the
distribution of sodium chloride within the hide. Next, we
evaluated the effect that commercial degreasers exerted on
the penetration of salt into the hide, as well as their fat

JALCA. VOL. 104, 2009
BRINE CURING ADDITIVES                                                    171

Determination of Moisture and Ash Content                         were processed and analyzed using Fovea 3.0 plug-ins
An oval arch punch (C.S. Osborne & Co., Harrison. NJ), 7/8        (Reindeer Graphics, Asheville, NC) for PhotoShop, v. 7
inches (2.2 cm) in diameter, was used to sample the pieces of     (Adobe Systems, Inc., San Jose, CA). The montages were
hide. Samples were clipped to minimize variability due to         spatially filtered with a Gaussian blur (3 pixels) to reduce
long hair. Next, they were weighed on an analytical balance       local noise and a line profile was drawn in each image
into dry tared crucibles and dried in a vacuum oven at 80 °C      extending from a point at the grain surface to a point at the
for 18 h. After cooling in a desiccator they were weighed         flesh surface. The line profiles were then plotted as gray
and percentage moisture was calculated. Dry samples were          level versus distance (data not shown), and the ranges of gray
placed in a muffle furnace and ashed at 600 °C for 2 h. After     levels for different curing times were plotted in Figure 3.
cooling in a desiccator, they were weighed and percentage
ash was calculated. All samples were run at least in              Statistical Analysis
triplicate.                                                       Data were analyzed by analysis of variance followed by a
                                                                  Dunnett's test to compare each treatment (degreasing agent)
Determination of Fat Content                                      with the control. Further comparisons were made using
In order to accurately compare results among different            orthogonal polynomial contrasts to test the linear and
samples, fat content' is expressed in terms of moisture and       quadratic trends due to degreaser 1 concentration. An
ash free basis (MAFB).9 All samples were run in triplicate.       orthogonal contrast was also used in the sophorolipid study
                                                                  to determine the significance of the filtering effect.
Determination of Thermal Stability
Differential scanning calorimetry (DSC) analysis was
performed on a Multi-Cell Differential Scanning Calorimeter                      RESULTS AND DISCUSSION
CSC-4 100 (Calorinietry Sciences Corporation, Lindon, UT).
An aliquot of raw or cured hide of approximately 100 mg          Stratigraphic Study
was weighed into a stainless steel pan and placed in the         The layer-wise distribution of water and salt (ash) in a hide
calorimeter. Another pan containing approximately the            cured for various intervals of time was monitored (Figures la
same weight of a 5% NaCI solution was used as a reference.       and Ib). Typically, the flesh layer included the flesh itself
When raw hide samples were analyzed, nanopure water was          and the attached adipose tissue; the middle layer represented
used as a reference. Both sample and reference capsules          the majority of the corium or true skin; and the grain layer
were weighed before and after the DSC run in order to            included the junction of grain and corium and the epidermis.
determine any possible weight loss by leakage. Samples           The initial moisture content was highest in the region of the
were heated from 10°C to 120°C at 1.5 °C/min. The peak           epidermis and decreased toward the center of the corium.
maximum temperature was taken as the hide's denaturation         Whereas the diminishing moisture content of the flesh layer
temperature (T1)). All samples were run in duplicate.            leveled off at 54% after 2 h of cure, the moisture content of
                                                                 the middle and grain layers continued to diminish over a
Back-scattered/Low Vacuum Scanning Electron                      24-h period to less than 45% (Figure la). The salt content of
Microscopy (SEM-BSE)                                             a raw hide was found to be less than a 0.5%. As curing
Backscattered electrons consist of high-energy electrons         progressed, salt content increased in all three strata: the flesh
originating in the electron beam that are reflected or           layer contained the highest amount of salt at all curing times
backscattered out of the specimen interaction volume. The        (Figure lb). Noteworthy, the salt content of the flesh layer
brightness of the SEM-BSE image tends to increase with the       after 30 min and 1 h of cure was 6.7 and 7.1%, respectively,
atomic number. Two major advantages over conventional            but only 1.6 and 1.9%, respectively, in the grain layer.
SEM in the secondary electron image mode are the high-
quality atomic number contrast images produced and the           These figures demonstrated that salt entered the hide mainly
simplicity of the technique, which does not require a            from the flesh side, which is in agreement with the findings
conductive coating.''                                            of McLaughlin and Theis." It was also confirmed that the
                                                                 epidermis acted as a semipermeable membrane, which
A piece of raw hide of approximately 1 x 1 in (2.5 x 2.5 cm)     allowed the withdrawal of water by osmosis but did not
was immersed in a beaker containing 500% v/v float of a          allow salt to penetrate through it. 12 Thus, whereas water was
saturated brine solution and gently agitated for varying         extracted from the hide by both sides, only the flesh side was
intervals of incubation time. A 2-3 mm wide slice of the         susceptible to extensive absorption of salt, which then
sample was excised manually with a stainless steel razor         diffused into the hide and towards the grain. The porous
blade (cutting from flesh surface toward the grain), mounted     nature of the hide may have also contributed to the diffusion
on aluminum stubs, and then irradiated at an accelerating        of salt through the hide by capillarity.
voltage of 25 kV in low vacuum mode (spot size 3.0,
pressure 0.98 Torr) using a Quanta 200 FEG environmental         By means of the equation,
scanning electron microscope (FEI Company, Hillsboro,
OR). Samples were imaged as montages at a magnification            Saturation    = (%A>/ .                                    100
of 50 x . Individual montages of images at each curing time                                   sture ).
                                                                                            %Mot
                                                                                              	              ( , '3 -9
                                                                                                           JALC4, VOL 104, 2009
172                                                                                     BRINE CURING ADDITIVES


                                                                         (a)                                 the hide salt saturation levels at various curing times were
                                                                                                             calculated (Figure lc). O'Flaherty' 3 claimed that a 70% salt
                             	                                                                               saturation of the water remaining in the hide with a maximum
                      70                                                          -- Flesh layer
                                           	
                                      i.                                           • Midcle layer            of 50% moisture was needed for a proper cure. Later on, a
                       	
            Q-) U
                                                                                ---4---- Grain layer         new minimum standard of 85% salt saturation was established
                      60	                          •                                                         by the U.S. Hide, Skin & Leather Association.' 4 The salt
                                               £                                                             saturation of the flesh layer was the highest of all three layers
                      55	                               --                                                   at all curing times. The reason was found in the rapid
            U,                                                                                               dehydration experienced in the early stages of the cure along
            0
            E                                                                                                with the almost exclusive penetration of salt from the flesh
            a) 45                                                                                            side of the hide. The differences of hide salt saturation levels
                      40                                                                                     among the three layers become less pronounced after 16 h of
                                                                                                             cure. Although we did not sample the hides beyond the 24 h
                      35                                                                                     curing time frame, one could assume that the hide and
                                                             	
                                  0	                    4         8	      12	       16	      20	       24    surrounding brine reached equilibrium after about one day of
                                                                       Time (h)                              brining. In fact, it was previously reported that a hide
                                                                                                             continuously brined for 48 h took up moisture as well as
                                                                                                             salt ;4 ' 5 brining a hide beyond the equilibrium did not
                                                                                                             necessarily entail a more proper cure.
                                                                        (t)
                      20
                                                                                                            The denaturation or melting temperature (T,) of the grain,
                                                                                                            middle and flesh layers of a hide cured for various time
                                                                                                            intervals was monitored (Figure 2). The hide's collagen,
                      15                                                                                    upon heating, undergoes a transition from the triple helix to
            C                                                                                               a randomly coiled form in which the three chains are
            a-)
            C
                                                                                                            separated.' 6 The flesh layer was the first to reach a constant
                      10                                                                                    T0 of 78 °C after only 2 h of cure. On the other hand, about
        4::
            (4,
                                                                                                            8 h of cure were needed to level off the temperature curve of
            f3
                                                                                                            the middle and grain layers IT = 82 °C). The increase of the
            CD
        -o                                                                                                  thermal stability of the hide upon brining could be ascribed
                                                                                                            to two factors. The first and most important factor is the
                                                                                                            dehydration of the hide. Kopp et al. 17 developed a
                                                                                                            mathematical function that showed an exponential decrease
                                                                                                            ofT0 with increasing moisture content. The second factor is
                                 0	                    4	        8	      12	        16	      20	       24   protein salting out and aggregation. The brine, despite the
                                                                       Time (h)                             disruption of some hydrogen bonds due to the withdrawal of
                                                                                                            water, induces this phenomenon, which was reported to
                                                                                                            further stabilize the collagen molecules, thus increasing the
                                                                         (c)                                values of TD.'8
                  100
                                                                                                                   85
                                                                                                                                                     U
            _- 80
            C     -                                                                                                80                                -	-              	             -1
            0                                           de                                                                    A	                 '
                      60                                                                                                      1
                                                                                                                   75 A	                    .	                                      -

                      40                                                                                      a	                   -
                                                                                                             i—
            U)                                                                                                     70	                                                              -
                                                       ZFlesh layer
            a)
       '	             20
                                                               Middle layer                                                                                        -- Flesh layer
                                                               Grain layer                                         65	                                               I Middle layer -
                                                                                                                                                                  ---.--- Grain layer
                       [I]
                                                                                                                   60	                               I	      I	           I
                                  0	                   4	        8	      12	        16	      20	       24
                                                                       Time (h)                                          0	            4	            8	     12	      16	      20	   24
                                                                                                                                                          Time (h)
    Figure 1: Stratigraphic distribution of (a) water (b) ash and (c) hide salt	
                                                                                                            Figure 2: Denaturation temperature (T 1) ) of the grain, middle, and flesh
    saturation in a hide treated for various intervals of time with a 500% float 	
                                                                                                            layers of a hide treated for various intervals of time with a 500% float
    of an initial 95 'SAL. Each point is the mean of three values,	
                                                                                                            of an initial 95 'SAL brine. Each point is the mean of two values.
      JALCA, VOL. 104, 2009
BRINE CURING ADDITIVES                                                    173


                                                                                                 above 200 (16 h), and the higher values were located within
                                                                                                 the flesh side of the cross-section, with a boundary slowly
                                                                                                 moving toward the grain side of the cross-section as the
                                                                                                 hours of curing increased (Figure 3).

                                                                                                 Degreasing Study
                                                                                                 The effect of three commercial degreasers on the content of
                                                                                                 water, salt and extractable fat of the hide after 16 h of brine
                                                                                                 curing was evaluated (Table I). A degreaser concentration of
                                                            t.•è                                 0.5% (w/w) with respect to the combined weight of hide and
                -	         -	
                                                               '-	    I                          brine was used. Samples that had been brine-cured in the
          h                                                                                      presence of degreaser I showed a significantly higher salt
                                                                                                 content than the control, to which no degreaser had been
                      -	                              ,.	     ..
                                                                                                 added. Furthermore, degreaser I was shown to be the most
                                                                                                 efficient as far as its fat-removal capacity, significantly

                                'J                                                               decreasing the extractable fat content with respect to the
                                                                                                 control. Samples that had been treated with degreasers 2 and
                                                                                                 3, despite tending to increase salt content and decrease
                                                                                                 extractable fat, were not statistically more efficient than the
                                                                                                 control. The composition of degreasers 2 and 3 was likely
                                                                                                 the cause of a lower efficiency than degreaser I. Although
      NLIIi2.tIU:
                                                                                                 the specific compositions of these commercial products are
                                                                                                 not disclosed, they are typically composed of a blend of
           Bck-ttr	             CT(Cring time in horn)	      GIK (C.rny Iei rne)                 nonionic surfactants, modifiers and adjuvants. The
    Figure 3: Composite images of hide samples, collected at different cur-
                                                                                                 hydrophilic-lipophilic balance (HLB) is a widely used scale
    ing times by low vacuum, mixed signal SEM imaging. Image heights                             in the technology of surfactants; HLB values run from 0 to
    were adjusted to an average value in order to facilitate comparisons. At                     20 and indicate whether a surfactant has greater wetting (low
    0 hours (control), the superficial brightness was low and variable in the                    end of the scale) or emulsifying properties (high end of the
    lower, flesh side and uniformly brighter in the upper, grain side the                        scale). It is likely that degreaser I had a slightly higher HLB
    range of gray levels was narrow, between 69 and 77. At 1-24 hours of                         than the other two products and hence a higher tendency
    curing, the average values of brightness were increased almost mono-                         toward forming oil-in-water emulsions. As a matter of fact,
    tonically, mainly from the flesh side, but not uniformly some bright                         the emulsification of fat in water was reported to be a crucial
    and dark patches were present through 1, 2, 4, 8 and 16 hours. At 24
                                                                                                 step for the efficiency of the degreasing process.'9
    hours, the brightness was the most uniform, suggesting that the concen-
    trations of Na and Cl were evenly distributed in the hide.
                                                                                                Next, degreaser 1 was selected to study the effect of its
                                                                                                concentration on the content of water, salt and extractable fat
    Cross-sectioned samples of hides, cured up to 24 It duration,                               of a hide after 16 h of curing with brine (Table II). All three
    were examined in a scanning electron microscope using a                                     tested concentrations of degreaser (0.25, 0.5 and I% w/w)
    backscatter detector at low vacuum. Although the backscatter                                significantly defatted the hide. Furthermore, hides treated
    signal is not specific for sodium chloride, results of                                      with a concentration of 0.5% also had significantly higher
    backscattered intensity variations were expected to reveal                                  salt and salt saturation values. The statistical analysis
    general trends related to diffusion of the dissolved salt that                              showed evidence of a significant quadratic trend with
    could be further explored and mapped by energy dispersive                                   increasing concentration of degreaser 1, with a maximum
    x-ray microanalysis.                                                                        occurring at a critical concentration between 0.5% and 1%.
                                                                                                The usage of a concentration larger than this critical point
    The range of intensity in backscattered images was adjusted                                 neither further increased the uptake of salt nor additionally
    to maximize the dynamic range of the detector by adjusting                                  decreased the fat content. That could be ascribed to the fact
    contrast and brightness values with the waveform monitor                                    that the concentration of surfactants in degreaser 1 was well
    using the 24-h cured sample. Then images of all the cured                                   above the critical micelle concentration.
    samples were collected under the same conditions. Line
    profiles drawn on images front grain side to flesh side of                                  The feasibility of using a sophorolipid (SL; a fermentation
    an uncured hide (0 h) had a narrow range of low brightness                                  product, under investigation at this location) as a degreasing
    values (69-77) relative to the values set for the 24-h sample.                              agent for raw hides was examined. Due to the low solubility
    At 0 h, higher values were located in the lower half or flesh-                              of SL in the brine, the effect of filtering the SL solution prior
    side of the hide. Similar line profiles drawn on backscatter                                to its use was also examined. By doing this, we ensured that
    images of cured hides indicated that the range of intensities                               the brine solution contained the maximum amount of soluble
    increased monotonically w'th longer curing times, with                                      SL. Hide samples cured with the unfiltered brine-SL solution
    brightness values extending from a low around 20 to a high                                  displayed significantly higher values of salt and salt saturation

                                                                                                                                          /AICA, VOL 104, 2009
174	                                             BRINE CURING ADDITIVES




                                                        TABLE I
                           Effect of Commercial Degreasers on Brine Curing 10.5% w/wI
           Treatment	            Moisture (%)	     Salt (%)	        Hide salt saturation(%)	    Fat (%, MAFB)
        Control	                   46.5 + 1.5	     11.8 ± 0.9	              70.9 ± 7.0	             11.8 ± 2.6
        Degreaser 1	               47.9 ± 3.0	     12.9 ± 0.9*	             75.2 ± 1.1	              7.3 + 0.6
        Degreaser 2	               46.5 ± 1.0	     12.1 ± 0.8	              72.1 ± 4.1	              8.8 ± 3.6
                       	                                                                 	
        Degreaser 3                46.7 + 1.7	     12.2 ± 0.4	              73.1 ± 4.1               8.8 ± 2.2

        Average of 8 values

        Values with * are significantly different from the control (Dunnett's test, p<0.05)




                                                       TABLE H
                                        Effect of Degreaser 1 on Brine Curing
         Treatment	             Moisture (%)	     Salt (%)	        Hide salt saturation (%)	   Fat (%, MAFB)
 Control	                         53.4 ± 2.0	     15,2 ± 0.6	              79.5 ± 1.3	            16.8 ± 2.2
 Degreaser 1 [0.25%]	             50.4 ± 2.0	     13.8 ± 1.1	              76.3 + 3.5	              7.4 ± 2.4
 Degreaser 1 [0.5%]	              57.2 ± 4.2	     17.1 ± 1.7*	             83.5 ± 2.7*	             3.8 + 0.9*
 Degreaser 1 [1%]	                56.4 ± 2.9	     16.5 + 0.7	              81.7 ± 1.9	              9.7 ± 2,9*
 Average of 6 values

 Values with * are significantly different from the control (Dunnett's test, p<0.05)




                                                      TABLE LII
                                       Effect of Sophorolipid on Brine Curing
         Treatment	            Moisture (%)	     Salt (%)	        Hide salt saturation (%)     Fat (%, MAFB)
   Control	                      45.0± 1.4	      11.8+0.6	               72.8± 1.5               15.3 ± 0.5
   SL Non-filtered	             46.6 ± 0.8	      12.5 ± 0.3*	            74.9 + 0.8*              9.1 ± 2.3*
   SL filtered	                 49.7± 1 . 6*	    13.0±0.5*	              73.0± 1.1                11.1 ± 1.9*
   Average of 5 values

   Values with * are significantly different from the control (Dunnett's test, p<0.05)



JALCA, VOL. 104, 2009
BRINE CURING ADD[ FIVES                                                   175


than the control (Table Ill). The extractable fat was also            findings were corroborated by the pictures taken with a
significantly lower than the control. When a filtered brine-          scanning electron microscope run in the back-scattered
SL was used, the values for moisture, salt, and extractable fat       electron mode. Furthermore, the thermal stability of the hide
content were significantly different from those of the control.       increased upon curing, mainly due to the simultaneous
Hence, SLs were demonstrated to have a degreasing activity            dehydration and salting out processes of the constituent
on the hide. The percentage of fat removed from the hide              collagen. If 0.5% (w/w) of a commercial degreaser, made of
was 40.5 and 27.5% for the unfiltered and filtered SL-brine           a blend of nonionic surfactants, had been added to the brine,
solution, respectively. These figures are similar to those            the fat content of that hide was significantly decreased and
obtained for the commercial degreasers (from 25.4% for                the uptake of salt was also significantly enhanced. Since
degreasers 2 and 3 to an average of 53.4% for degreaser 1).           another two commercial degreasers exhibited less stimulation
The undissolved SL likely provided a reservoir of active              of salt uptake, we concltided that the composition of the
surfactant as the initial concentration of solubilized SL             degreaser was a critical parameter for this specific purpose.
suffered from dilution or inactivation.                               The sophorolipid tested showed remarkable degreasing
                                                                      properties and enhanced the uptake of salt by the hide if it
From Tables I, II and III it can be seen that test samples with       was used above the solubility limit. These facts along with
a significantly higher amount of salt than the controls also          its low-foam properties and low cost (from $1 to 3/kg;22)
exhibited a significantly lower fat content. However, this            make it an attractive choice of surfactant. One may
statement was not verified in the other direction. It was also        hypothesize that the addition of small amounts of a proteolytic
observed that a significant effect of the degreaser on the            enzyme along with a degreasing agent would enhance the fat
content of salt and fat did not necessarily entail a significant      removal action, since it would facilitate the breakdown of the
increase in the salt saturation levels. That could be attributed      proteinaceous membrane of the fat-containing sac .21
to the wetting properties of the degreasers, which did not            Nevertheless, the detrimental effect that this treatment could
significantly alter the amount of remaining moisture in the           have on the grain is an important drawback.
hide after the 16 h curing time frame (Tables I and 11).
                                                                      In this paper, we gave an overview of the brine curing
 It is important to bear in mind that the results presented in        process of raw hides and also suggested the use of an additive
this study are based on the analysis run on different areas of        (e.g., commercial degreasers, sophorolipid) to enhance the
two cow hides. Variance in the results can be attributed to           uptake of salt and remove a major amount of the fat. It is
some extent to the variability always found in biological             important to note that actual raceways or vats are operated
 material. III              although the hides were washed,           continuously. Thus, it will be essential to find a way to
 fleshed, cut up and stored in the freezer on the same day that       remove the fat that builds up in the vat.
the animal was slaughtered, some damage to the hide due to
a delayed cure might have taken place. A delayed cure of
only a few hours was reported to slow down the diffusion of                             ACKNOWLEDGEMENTS
salt during the early stages of the cure' Furthermore, and
for the particular case of fat content, some variability could        The authors appreciate the assistance of the following: Dr.
be attributed to the horizontal distribution of grease, which is      Richard Ashby, Guoping Bao, Dr. Eleanor Brown, Nicholas
more abundant in the looser and more flexible areas (e.g.,            Latona, Joe Lee, Dr. Justin Martin, Paul Pierlott, Dr. Daniel
belly; 20). Despite all these facts, the coefficients of variation    Solaiman, Maryann Taylor and Amanda Tiscavitch.
(CV) obtained for the determination of moisture, salt and salt
saturation were 3.97, 5.76 and 3.54%, respectively, which
indicate good precision." In the particular case of the                                       REFERENCES
determination of extractable fat, a CV of 21.3% was
relatively precise, considering the low analytical values of
                                                                       I. Personal communication, Ed Godsalve, WE CO., 1991,
that parameter.
                                                                          Inc., 2006.
                                                                      2. Rajamani, S. Cleaner tanning technologies in the beam
                                                                          house operation. UNEDO report. pp. 9-18, 1998,
                        CONCLUSIONS
                                                                      3. Hernàndez Balada, E.; Marmer, W.N.; KolomaznIk, K.;
The purpose of research reported in this article was to                   Cooke, P.H.; Dudley, R.L. Mathematical model of raw
evaluate the possibility of using degreasers as brine curing              hide curing with brine. JALCA 103, 128-134, 2008.
additives, with the aim of enhancing the uptake of salt by the        4. Stuart, L.S.; Frey, R.W. Effect of adipose tissue fat on the
hide. In the stratigraphic study carried out in order to get a            green-salting of heavy hides. JALCA 35, 414-418, 1940.
better understanding of the curing process, we found that the         5. Stockman, GB.; Rangarajan, R.; Didato, D.T. The
epidermis acted as a semipermeable membrane, enabling the                 replacement of nonylphenolethoxylates (NPEs) as
diffusion of water from the hide and into the surrounding                 degreasing agents in wet blue manufacture. World Leather,
float as well as hindering the diffusion of salt into the hide,           October 2005.
which occurred from the flesh side overwhelmingly. These              6. Garcia, R.A.; Solaiman, D.K.Y. Government scientists
                                                                          find new uses for rendered products. Render, June 2008.

                                                                                                               JALcA, VOL. 104, 2009
176                                                  BRINE CURING ADDITIVES


7. Solainian, D. K. Y. Applications of microbial biosurfactants.    17. Kopp, J.: Bonnet, M.; Renou, J.P. Effect of collagen
   Inft.rm 16, 408-410, 2005.                                           crosslinking on collagen-water interactions (a DSC
8. Taylor, M.M.: Diefendorf, E.J.; Phillips, J.G.: Feairheller,         investigation). Matrix 9, 443-450, 1989.
   S. H.; Bailey, D.G. Wet process technology 1. Determination     18. Komsa-Penkova, R.; Koynova, R.; Kostov, G.; Tenchov,
   of precision for various analytical procedures. JALCA 81,            B.G. Thermal stability of calf skirt collagen type I in salt
   4-18, 1986.                                                          solutions. Biochim. Biophvs. Acta Protein Siruct. Mo!.
9. Donmez, K.; Kallenberger, W.E. Total crude fat                       Envmol. 1297, 171-181, 1996.
   determination in hides. JALCA 89. 369-390, 1994.                19. Thanikaivelan, P.; Rao, JR.; Nair, RU.: Rarnasarni, T.
10. Robinson. B.R.; Nickel, E.H. A useful new technique for             Progress and recent trends in biotechnological methods
    mineralogy: the backscattered-electron/low vacuum                   for leather processing. Trends Thotechnol. 22. 181-188,
    mode of SEM operation. Am. Mineral. 64, 1322-1328,                  2004.
     1979.                                                         20. Balderston, L. The distribution of grease in leather.
11. McLaughlin, G.D.; Theis, E.R. Science of hide curing.              JALCA 17, 405-407, 1922.
    JALCA 17, 376-399, 1922.                                       21. Taylor, M.M.; Diefendorf, E.J.; Artymyshyn, B.:
12. Tancous, J.J. A study of a drawn condition, caused                  Hannigan, MV.; Phillips, J.G.; Feairhcller, S.H.; Bailey,
    through osmosis, encountered in some brine-cured hides.             D.G. The chemical and physical analysis of contemporary
    JALCA 58, 143-154, 1963.                                            thru-blue tanning technology, 1984. Animal Biomaterials
13. O'Flaherty, F. Curing study part 1: Moisture to ash                 Laboratory, ERRC, Philadelphia, PA 19038. Available
    relationship. Leather and Shoes 138, 31-34, 1959.                   from senior author at maryann.taylor@ars.usda.gov .
14. Trade Practices for Proper Packer Cattlehide Delivery,         22. Sun, X.X.; Choi, J.K.; Kim, E.K. A preliminary study on
    3' ed., Leather Industries of America and U.S. Hide,               the mechanism of harmful algal bloom mitigation by use
    Skin & Leather Association, pp. 12-19, 1993.                       of sophorolipid treatment. J. Exp. Mar. Biol. Ecol. 304,
15. Strandine, E.J.; DeBeukelaer, F.L.; Werner, G.A.                    35-49, 2004.
    Stratigraphic distribution of sodium chloride and water        23. Langridge, D.A.; Long, A.J.; Addy, V.L. The impact of
    in fresh and brined steer hide. JALCA 46, 19-34, 1951.             sebaceous grease on the leather industry. JALCA 101,
16. Miles, CA.; Bailey, A.J. Thermal denaturation of                   45-50, 2006.
    collagen revisited. Proc. Indian Acad. Sci. (Chem. Sci.)
    111, 71-80, 1999.




JALcA, VOL. 104, 2009

More Related Content

What's hot

Characterization and Comparative Adsorption Studies of Activated Carbon and S...
Characterization and Comparative Adsorption Studies of Activated Carbon and S...Characterization and Comparative Adsorption Studies of Activated Carbon and S...
Characterization and Comparative Adsorption Studies of Activated Carbon and S...IRJET Journal
 
Tannery waste
Tannery wasteTannery waste
Tannery wasteJay Kumar
 
ERIKS RX Spill Control
ERIKS RX Spill ControlERIKS RX Spill Control
ERIKS RX Spill ControlSarah Evans
 
Dissolved air system and water treatment for drinkable waterl
Dissolved air system and water treatment for drinkable waterlDissolved air system and water treatment for drinkable waterl
Dissolved air system and water treatment for drinkable waterlSulistyo Rabono
 
A simple nonconventional method to extract amorphous silica from rice husk
A simple nonconventional method to extract amorphous silica from rice huskA simple nonconventional method to extract amorphous silica from rice husk
A simple nonconventional method to extract amorphous silica from rice huskGaurav Soni
 
Tanning industry waste
Tanning industry wasteTanning industry waste
Tanning industry wasteBharathM64
 
Dissolve air flotation technology to treat highly polluted wastewater
Dissolve air flotation technology to treat highly polluted wastewaterDissolve air flotation technology to treat highly polluted wastewater
Dissolve air flotation technology to treat highly polluted wastewaterIndia Water Portal
 
Properties of Cold Process Soaps Prepared from Different
Properties of Cold Process Soaps Prepared from Different Properties of Cold Process Soaps Prepared from Different
Properties of Cold Process Soaps Prepared from Different v2zq
 
PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...
PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...
PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...Repository Ipb
 
John Dunford - Bond Water Technologies - Dissolved Air Flotation (DAF) Over...
John Dunford  - Bond Water Technologies -  Dissolved Air Flotation (DAF) Over...John Dunford  - Bond Water Technologies -  Dissolved Air Flotation (DAF) Over...
John Dunford - Bond Water Technologies - Dissolved Air Flotation (DAF) Over...Jim Clarke
 
A comparison of chemical treatment methods for the preparation of rice husk c...
A comparison of chemical treatment methods for the preparation of rice husk c...A comparison of chemical treatment methods for the preparation of rice husk c...
A comparison of chemical treatment methods for the preparation of rice husk c...Agriculture Journal IJOEAR
 
Preparation of Poly Acrylate Binder
Preparation of Poly Acrylate Binder Preparation of Poly Acrylate Binder
Preparation of Poly Acrylate Binder Mainul Morshed
 
Daf brochure centerfold
Daf brochure centerfoldDaf brochure centerfold
Daf brochure centerfoldYanet Octavia
 

What's hot (20)

Characterization and Comparative Adsorption Studies of Activated Carbon and S...
Characterization and Comparative Adsorption Studies of Activated Carbon and S...Characterization and Comparative Adsorption Studies of Activated Carbon and S...
Characterization and Comparative Adsorption Studies of Activated Carbon and S...
 
Tannery waste
Tannery wasteTannery waste
Tannery waste
 
Tannery waste
Tannery wasteTannery waste
Tannery waste
 
Scouring
ScouringScouring
Scouring
 
ERIKS RX Spill Control
ERIKS RX Spill ControlERIKS RX Spill Control
ERIKS RX Spill Control
 
Dissolved air system and water treatment for drinkable waterl
Dissolved air system and water treatment for drinkable waterlDissolved air system and water treatment for drinkable waterl
Dissolved air system and water treatment for drinkable waterl
 
Production of mea triazine m1
Production of  mea triazine m1Production of  mea triazine m1
Production of mea triazine m1
 
A simple nonconventional method to extract amorphous silica from rice husk
A simple nonconventional method to extract amorphous silica from rice huskA simple nonconventional method to extract amorphous silica from rice husk
A simple nonconventional method to extract amorphous silica from rice husk
 
CT-3215
CT-3215CT-3215
CT-3215
 
Tanning industry waste
Tanning industry wasteTanning industry waste
Tanning industry waste
 
Dissolve air flotation technology to treat highly polluted wastewater
Dissolve air flotation technology to treat highly polluted wastewaterDissolve air flotation technology to treat highly polluted wastewater
Dissolve air flotation technology to treat highly polluted wastewater
 
Properties of Cold Process Soaps Prepared from Different
Properties of Cold Process Soaps Prepared from Different Properties of Cold Process Soaps Prepared from Different
Properties of Cold Process Soaps Prepared from Different
 
Training zbj
Training   zbjTraining   zbj
Training zbj
 
Tannery Industry
Tannery IndustryTannery Industry
Tannery Industry
 
Dry Process
Dry ProcessDry Process
Dry Process
 
PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...
PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...
PRODUCTION OF SEMICONDUCTOR MATERIALS SILICON FROM SILICA RICE HUSK WASTE AS ...
 
John Dunford - Bond Water Technologies - Dissolved Air Flotation (DAF) Over...
John Dunford  - Bond Water Technologies -  Dissolved Air Flotation (DAF) Over...John Dunford  - Bond Water Technologies -  Dissolved Air Flotation (DAF) Over...
John Dunford - Bond Water Technologies - Dissolved Air Flotation (DAF) Over...
 
A comparison of chemical treatment methods for the preparation of rice husk c...
A comparison of chemical treatment methods for the preparation of rice husk c...A comparison of chemical treatment methods for the preparation of rice husk c...
A comparison of chemical treatment methods for the preparation of rice husk c...
 
Preparation of Poly Acrylate Binder
Preparation of Poly Acrylate Binder Preparation of Poly Acrylate Binder
Preparation of Poly Acrylate Binder
 
Daf brochure centerfold
Daf brochure centerfoldDaf brochure centerfold
Daf brochure centerfold
 

Viewers also liked

Food Processing
Food ProcessingFood Processing
Food Processingjazzy31
 
Principles of fish preservation and processing
Principles of fish preservation and processingPrinciples of fish preservation and processing
Principles of fish preservation and processingSameer Chebbi
 
New economic policy
New economic policyNew economic policy
New economic policyasyapable
 
Fish processing ppt
Fish processing pptFish processing ppt
Fish processing pptGeeta12344
 
Fish Processing Learning Module
Fish Processing Learning ModuleFish Processing Learning Module
Fish Processing Learning ModuleBogs De Castro
 
Career planning and development
Career planning and developmentCareer planning and development
Career planning and developmentBinty Agarwal
 
Topic 10 economic development policy
Topic 10 economic development policyTopic 10 economic development policy
Topic 10 economic development policyChe Amm
 
Career Planning and Development
Career Planning and DevelopmentCareer Planning and Development
Career Planning and DevelopmentYodhia Antariksa
 
Introduction to economics
Introduction to economicsIntroduction to economics
Introduction to economicsMichael Noel
 

Viewers also liked (11)

Salt Lakes
Salt LakesSalt Lakes
Salt Lakes
 
Food Processing
Food ProcessingFood Processing
Food Processing
 
Topic 11 evaporite salt deposits
Topic 11 evaporite salt depositsTopic 11 evaporite salt deposits
Topic 11 evaporite salt deposits
 
Principles of fish preservation and processing
Principles of fish preservation and processingPrinciples of fish preservation and processing
Principles of fish preservation and processing
 
New economic policy
New economic policyNew economic policy
New economic policy
 
Fish processing ppt
Fish processing pptFish processing ppt
Fish processing ppt
 
Fish Processing Learning Module
Fish Processing Learning ModuleFish Processing Learning Module
Fish Processing Learning Module
 
Career planning and development
Career planning and developmentCareer planning and development
Career planning and development
 
Topic 10 economic development policy
Topic 10 economic development policyTopic 10 economic development policy
Topic 10 economic development policy
 
Career Planning and Development
Career Planning and DevelopmentCareer Planning and Development
Career Planning and Development
 
Introduction to economics
Introduction to economicsIntroduction to economics
Introduction to economics
 

Similar to Evaluation of degreasers as brine curing additives

Sludge digestor
Sludge digestor Sludge digestor
Sludge digestor MNIT,JAIPUR
 
determination of Acrylamide.pptx
determination of Acrylamide.pptxdetermination of Acrylamide.pptx
determination of Acrylamide.pptxRezaJoia
 
Mathematical model of raw hide curing with brine
Mathematical model of raw hide curing with brineMathematical model of raw hide curing with brine
Mathematical model of raw hide curing with brineEduard Hernàndez I PMP®
 
International Journal of Engineering and Science Invention (IJESI)
International Journal of Engineering and Science Invention (IJESI)International Journal of Engineering and Science Invention (IJESI)
International Journal of Engineering and Science Invention (IJESI)inventionjournals
 
summer training ppt_2_1
summer training ppt_2_1summer training ppt_2_1
summer training ppt_2_1Anam Khanam
 
Tannery industry (BE C)
Tannery industry (BE C)Tannery industry (BE C)
Tannery industry (BE C)Shubham Patil
 
Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...
Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...
Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...INFOGAIN PUBLICATION
 
Development of kinetic model for adsorption of carotenoids on activated clay ...
Development of kinetic model for adsorption of carotenoids on activated clay ...Development of kinetic model for adsorption of carotenoids on activated clay ...
Development of kinetic model for adsorption of carotenoids on activated clay ...eSAT Journals
 
Development of kinetic model for adsorption of
Development of kinetic model for adsorption ofDevelopment of kinetic model for adsorption of
Development of kinetic model for adsorption ofeSAT Publishing House
 
Presentation on Leather Industry
Presentation on Leather IndustryPresentation on Leather Industry
Presentation on Leather IndustryNiaz Memon
 
What is tanning? Overview of Leather Processing Process 2019
What is tanning? Overview of Leather Processing Process 2019What is tanning? Overview of Leather Processing Process 2019
What is tanning? Overview of Leather Processing Process 2019lambraven18
 
Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...
Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...
Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...BRNSS Publication Hub
 
Unit 1- Introduction of Tanning
Unit 1- Introduction of Tanning Unit 1- Introduction of Tanning
Unit 1- Introduction of Tanning pascchemistry
 
Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...
Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...
Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...ijtsrd
 
Treatment of tannery wastewater . susan
Treatment of tannery wastewater . susanTreatment of tannery wastewater . susan
Treatment of tannery wastewater . susananniesj
 
NACE Refinery Chemical Cleaning Study
NACE Refinery Chemical Cleaning StudyNACE Refinery Chemical Cleaning Study
NACE Refinery Chemical Cleaning Studymialeeka
 
Diccionario acuicultura
Diccionario acuiculturaDiccionario acuicultura
Diccionario acuiculturaEnglish 101
 
deflouridation.ppt
deflouridation.pptdeflouridation.ppt
deflouridation.pptRohma Yusuf
 

Similar to Evaluation of degreasers as brine curing additives (20)

Sludge digestor
Sludge digestor Sludge digestor
Sludge digestor
 
determination of Acrylamide.pptx
determination of Acrylamide.pptxdetermination of Acrylamide.pptx
determination of Acrylamide.pptx
 
Mathematical model of raw hide curing with brine
Mathematical model of raw hide curing with brineMathematical model of raw hide curing with brine
Mathematical model of raw hide curing with brine
 
International Journal of Engineering and Science Invention (IJESI)
International Journal of Engineering and Science Invention (IJESI)International Journal of Engineering and Science Invention (IJESI)
International Journal of Engineering and Science Invention (IJESI)
 
summer training ppt_2_1
summer training ppt_2_1summer training ppt_2_1
summer training ppt_2_1
 
Tannery industry (BE C)
Tannery industry (BE C)Tannery industry (BE C)
Tannery industry (BE C)
 
Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...
Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...
Managing the Quality of Chromium Sulphate during the Recycling From Tanning W...
 
Development of kinetic model for adsorption of carotenoids on activated clay ...
Development of kinetic model for adsorption of carotenoids on activated clay ...Development of kinetic model for adsorption of carotenoids on activated clay ...
Development of kinetic model for adsorption of carotenoids on activated clay ...
 
Development of kinetic model for adsorption of
Development of kinetic model for adsorption ofDevelopment of kinetic model for adsorption of
Development of kinetic model for adsorption of
 
NALINI PPT.pptx
NALINI PPT.pptxNALINI PPT.pptx
NALINI PPT.pptx
 
Presentation on Leather Industry
Presentation on Leather IndustryPresentation on Leather Industry
Presentation on Leather Industry
 
What is tanning? Overview of Leather Processing Process 2019
What is tanning? Overview of Leather Processing Process 2019What is tanning? Overview of Leather Processing Process 2019
What is tanning? Overview of Leather Processing Process 2019
 
Ph.D. in Chemical Engineering Presentation
Ph.D. in Chemical Engineering PresentationPh.D. in Chemical Engineering Presentation
Ph.D. in Chemical Engineering Presentation
 
Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...
Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...
Evaluation of Cordia Dichotoma gum as A Potent Excipient for the Formulation ...
 
Unit 1- Introduction of Tanning
Unit 1- Introduction of Tanning Unit 1- Introduction of Tanning
Unit 1- Introduction of Tanning
 
Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...
Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...
Enrichment of Omega 3 Fatty Acids using Urea Complexation Method to Enhance t...
 
Treatment of tannery wastewater . susan
Treatment of tannery wastewater . susanTreatment of tannery wastewater . susan
Treatment of tannery wastewater . susan
 
NACE Refinery Chemical Cleaning Study
NACE Refinery Chemical Cleaning StudyNACE Refinery Chemical Cleaning Study
NACE Refinery Chemical Cleaning Study
 
Diccionario acuicultura
Diccionario acuiculturaDiccionario acuicultura
Diccionario acuicultura
 
deflouridation.ppt
deflouridation.pptdeflouridation.ppt
deflouridation.ppt
 

More from Eduard Hernàndez I PMP®

Properties of biopolymers produced by transglutaminase treatment of wpi and g...
Properties of biopolymers produced by transglutaminase treatment of wpi and g...Properties of biopolymers produced by transglutaminase treatment of wpi and g...
Properties of biopolymers produced by transglutaminase treatment of wpi and g...Eduard Hernàndez I PMP®
 
Whey Protein Isolate: a potential filler for the leather industry
Whey Protein Isolate: a potential filler for the leather industryWhey Protein Isolate: a potential filler for the leather industry
Whey Protein Isolate: a potential filler for the leather industryEduard Hernàndez I PMP®
 
Ph.D Thesis - Improvement of Conventional Leather Making Processes
Ph.D Thesis - Improvement of Conventional Leather Making ProcessesPh.D Thesis - Improvement of Conventional Leather Making Processes
Ph.D Thesis - Improvement of Conventional Leather Making ProcessesEduard Hernàndez I PMP®
 

More from Eduard Hernàndez I PMP® (6)

Properties of biopolymers produced by transglutaminase treatment of wpi and g...
Properties of biopolymers produced by transglutaminase treatment of wpi and g...Properties of biopolymers produced by transglutaminase treatment of wpi and g...
Properties of biopolymers produced by transglutaminase treatment of wpi and g...
 
Whey Protein Isolate: a potential filler for the leather industry
Whey Protein Isolate: a potential filler for the leather industryWhey Protein Isolate: a potential filler for the leather industry
Whey Protein Isolate: a potential filler for the leather industry
 
Biocarb Ox
Biocarb Ox Biocarb Ox
Biocarb Ox
 
M Sc Presentation
M Sc   PresentationM Sc   Presentation
M Sc Presentation
 
Ph.D Thesis - Improvement of Conventional Leather Making Processes
Ph.D Thesis - Improvement of Conventional Leather Making ProcessesPh.D Thesis - Improvement of Conventional Leather Making Processes
Ph.D Thesis - Improvement of Conventional Leather Making Processes
 
Renewable fillers for leather
Renewable fillers for leatherRenewable fillers for leather
Renewable fillers for leather
 

Recently uploaded

Measures of Central Tendency: Mean, Median and Mode
Measures of Central Tendency: Mean, Median and ModeMeasures of Central Tendency: Mean, Median and Mode
Measures of Central Tendency: Mean, Median and ModeThiyagu K
 
Russian Call Girls in Andheri Airport Mumbai WhatsApp 9167673311 💞 Full Nigh...
Russian Call Girls in Andheri Airport Mumbai WhatsApp  9167673311 💞 Full Nigh...Russian Call Girls in Andheri Airport Mumbai WhatsApp  9167673311 💞 Full Nigh...
Russian Call Girls in Andheri Airport Mumbai WhatsApp 9167673311 💞 Full Nigh...Pooja Nehwal
 
BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...
BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...
BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...Sapna Thakur
 
Web & Social Media Analytics Previous Year Question Paper.pdf
Web & Social Media Analytics Previous Year Question Paper.pdfWeb & Social Media Analytics Previous Year Question Paper.pdf
Web & Social Media Analytics Previous Year Question Paper.pdfJayanti Pande
 
The basics of sentences session 2pptx copy.pptx
The basics of sentences session 2pptx copy.pptxThe basics of sentences session 2pptx copy.pptx
The basics of sentences session 2pptx copy.pptxheathfieldcps1
 
The Most Excellent Way | 1 Corinthians 13
The Most Excellent Way | 1 Corinthians 13The Most Excellent Way | 1 Corinthians 13
The Most Excellent Way | 1 Corinthians 13Steve Thomason
 
APM Welcome, APM North West Network Conference, Synergies Across Sectors
APM Welcome, APM North West Network Conference, Synergies Across SectorsAPM Welcome, APM North West Network Conference, Synergies Across Sectors
APM Welcome, APM North West Network Conference, Synergies Across SectorsAssociation for Project Management
 
JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...
JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...
JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...anjaliyadav012327
 
Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...
Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...
Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...EduSkills OECD
 
1029-Danh muc Sach Giao Khoa khoi 6.pdf
1029-Danh muc Sach Giao Khoa khoi  6.pdf1029-Danh muc Sach Giao Khoa khoi  6.pdf
1029-Danh muc Sach Giao Khoa khoi 6.pdfQucHHunhnh
 
SOCIAL AND HISTORICAL CONTEXT - LFTVD.pptx
SOCIAL AND HISTORICAL CONTEXT - LFTVD.pptxSOCIAL AND HISTORICAL CONTEXT - LFTVD.pptx
SOCIAL AND HISTORICAL CONTEXT - LFTVD.pptxiammrhaywood
 
Arihant handbook biology for class 11 .pdf
Arihant handbook biology for class 11 .pdfArihant handbook biology for class 11 .pdf
Arihant handbook biology for class 11 .pdfchloefrazer622
 
Call Girls in Dwarka Mor Delhi Contact Us 9654467111
Call Girls in Dwarka Mor Delhi Contact Us 9654467111Call Girls in Dwarka Mor Delhi Contact Us 9654467111
Call Girls in Dwarka Mor Delhi Contact Us 9654467111Sapana Sha
 
Interactive Powerpoint_How to Master effective communication
Interactive Powerpoint_How to Master effective communicationInteractive Powerpoint_How to Master effective communication
Interactive Powerpoint_How to Master effective communicationnomboosow
 
A Critique of the Proposed National Education Policy Reform
A Critique of the Proposed National Education Policy ReformA Critique of the Proposed National Education Policy Reform
A Critique of the Proposed National Education Policy ReformChameera Dedduwage
 
Software Engineering Methodologies (overview)
Software Engineering Methodologies (overview)Software Engineering Methodologies (overview)
Software Engineering Methodologies (overview)eniolaolutunde
 
Grant Readiness 101 TechSoup and Remy Consulting
Grant Readiness 101 TechSoup and Remy ConsultingGrant Readiness 101 TechSoup and Remy Consulting
Grant Readiness 101 TechSoup and Remy ConsultingTechSoup
 

Recently uploaded (20)

INDIA QUIZ 2024 RLAC DELHI UNIVERSITY.pptx
INDIA QUIZ 2024 RLAC DELHI UNIVERSITY.pptxINDIA QUIZ 2024 RLAC DELHI UNIVERSITY.pptx
INDIA QUIZ 2024 RLAC DELHI UNIVERSITY.pptx
 
Measures of Central Tendency: Mean, Median and Mode
Measures of Central Tendency: Mean, Median and ModeMeasures of Central Tendency: Mean, Median and Mode
Measures of Central Tendency: Mean, Median and Mode
 
Russian Call Girls in Andheri Airport Mumbai WhatsApp 9167673311 💞 Full Nigh...
Russian Call Girls in Andheri Airport Mumbai WhatsApp  9167673311 💞 Full Nigh...Russian Call Girls in Andheri Airport Mumbai WhatsApp  9167673311 💞 Full Nigh...
Russian Call Girls in Andheri Airport Mumbai WhatsApp 9167673311 💞 Full Nigh...
 
BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...
BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...
BAG TECHNIQUE Bag technique-a tool making use of public health bag through wh...
 
Web & Social Media Analytics Previous Year Question Paper.pdf
Web & Social Media Analytics Previous Year Question Paper.pdfWeb & Social Media Analytics Previous Year Question Paper.pdf
Web & Social Media Analytics Previous Year Question Paper.pdf
 
The basics of sentences session 2pptx copy.pptx
The basics of sentences session 2pptx copy.pptxThe basics of sentences session 2pptx copy.pptx
The basics of sentences session 2pptx copy.pptx
 
The Most Excellent Way | 1 Corinthians 13
The Most Excellent Way | 1 Corinthians 13The Most Excellent Way | 1 Corinthians 13
The Most Excellent Way | 1 Corinthians 13
 
APM Welcome, APM North West Network Conference, Synergies Across Sectors
APM Welcome, APM North West Network Conference, Synergies Across SectorsAPM Welcome, APM North West Network Conference, Synergies Across Sectors
APM Welcome, APM North West Network Conference, Synergies Across Sectors
 
Mattingly "AI & Prompt Design: Structured Data, Assistants, & RAG"
Mattingly "AI & Prompt Design: Structured Data, Assistants, & RAG"Mattingly "AI & Prompt Design: Structured Data, Assistants, & RAG"
Mattingly "AI & Prompt Design: Structured Data, Assistants, & RAG"
 
Mattingly "AI & Prompt Design: The Basics of Prompt Design"
Mattingly "AI & Prompt Design: The Basics of Prompt Design"Mattingly "AI & Prompt Design: The Basics of Prompt Design"
Mattingly "AI & Prompt Design: The Basics of Prompt Design"
 
JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...
JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...
JAPAN: ORGANISATION OF PMDA, PHARMACEUTICAL LAWS & REGULATIONS, TYPES OF REGI...
 
Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...
Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...
Presentation by Andreas Schleicher Tackling the School Absenteeism Crisis 30 ...
 
1029-Danh muc Sach Giao Khoa khoi 6.pdf
1029-Danh muc Sach Giao Khoa khoi  6.pdf1029-Danh muc Sach Giao Khoa khoi  6.pdf
1029-Danh muc Sach Giao Khoa khoi 6.pdf
 
SOCIAL AND HISTORICAL CONTEXT - LFTVD.pptx
SOCIAL AND HISTORICAL CONTEXT - LFTVD.pptxSOCIAL AND HISTORICAL CONTEXT - LFTVD.pptx
SOCIAL AND HISTORICAL CONTEXT - LFTVD.pptx
 
Arihant handbook biology for class 11 .pdf
Arihant handbook biology for class 11 .pdfArihant handbook biology for class 11 .pdf
Arihant handbook biology for class 11 .pdf
 
Call Girls in Dwarka Mor Delhi Contact Us 9654467111
Call Girls in Dwarka Mor Delhi Contact Us 9654467111Call Girls in Dwarka Mor Delhi Contact Us 9654467111
Call Girls in Dwarka Mor Delhi Contact Us 9654467111
 
Interactive Powerpoint_How to Master effective communication
Interactive Powerpoint_How to Master effective communicationInteractive Powerpoint_How to Master effective communication
Interactive Powerpoint_How to Master effective communication
 
A Critique of the Proposed National Education Policy Reform
A Critique of the Proposed National Education Policy ReformA Critique of the Proposed National Education Policy Reform
A Critique of the Proposed National Education Policy Reform
 
Software Engineering Methodologies (overview)
Software Engineering Methodologies (overview)Software Engineering Methodologies (overview)
Software Engineering Methodologies (overview)
 
Grant Readiness 101 TechSoup and Remy Consulting
Grant Readiness 101 TechSoup and Remy ConsultingGrant Readiness 101 TechSoup and Remy Consulting
Grant Readiness 101 TechSoup and Remy Consulting
 

Evaluation of degreasers as brine curing additives

  • 1. 169 EVALUATION OF DEGREASERS AS BRINE CURING ADDITIVES b EDUARD HERNANDEZ BALADA, WILLIAM N. MARMER', PETER H. COOKE, AND JOHN C. PHILLIPS U.S. Department of Agriculture, Agricultural Research Service Eastern Regional Research Center 600 EAST MERMAID LANE, WYNDMOOR, PA 19038 USA ABSTRACT RESUMEN The length of time needed for brine curing of raw El tienipo requerido en la preservacion de pieles hides and skins, a minimum of 18 h, is a time- crudas por la acción de salmuera, un mInimo de 18 consuming process. In this paper we initially report horas, es un proceso que consume tiempo. En este the results of an investigation of the stratigraphic trabajo reportamos inicialmente los resultados de distribution of sodium chloride and water in fleshed una investigaciOn estratigralica de Ia distribución hides cured for varying intervals of time. We del cloruro de sodio y del agua en pieles previamente demonstrated that salt entered the hide mainly from descarnadas y tratadas durante diferentes intervalos. the flesh side. Water, on the other hand, was Hemos demostrado que la sal penetro La piel withdrawn from both sides of the hide; the epidermis principalmente por el lado de la came. El agua, acted as a semipermeable membrane. Three diferenternente, fue extrafda a través de ambas commercial degreasers as well as a glycolipid direcciones en la piel; la epidermis se comporto surfactant (sophorolipid) were tested as brine curing como una membrana semipermeable. Tres additives and their efficiency evaluated according desengrasantes comerciales asI como también un to the moisture, salt, salt saturation and fat content tensoactivo glucolIpido (soforolIpido) fueron levels in the brine-cured hide. One of the commercial ensayados como aditivos auxiliares para la degreasers, when used at 0.5% w/w, significantly preservación por sairnuera y su eficacia evaluada de removed fat from the hide as well as enhanced the acuerdo a los valores determinados por la huinedad, uptake of salt. The sophorolipid also was an sal, saturación salina, y contenido degrasa en la effective degreasing agent, decreasing the fat piel preservada por salmuera. Uno de los content of the brine-cured hide and, if used in desengrasantes, cuarido se utilizó at 0.5% en peso, excess, significantly increasing the uptake of salt. significativamente deserigrasO la piel asI como The data presented here confirmed that the usage of aumentó la absorción de la sal. El soforolIpido fue an appropriate degreasing agent in the brine is a también un efectivo desengrasante, disminuyendo suitable option for reducing the turn-around el contenido graso de la piel tratada por salmuera y, times in raceways and thus creating additional SI su ernpleo fuese en exceso, significativamente curing capacity. aumentarfa también la absorción de sal. Los datos aquI presentados confirmaron que el uso de desengrasantes en la salmuera es una opción apropiada para reducir ci tiempo de rotación en los tanques de salazón y asf aunientar la capacidad adicional del proceso de preservación. a Current address: Department of Chemical Engineering, University of Barcelona, Marti i Frallquès 1, 08028 Barcelona, Spain Corresponding author e-mail address: William.Marmer@ars.usda.gov Mention of trade names or commercial products in this article is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. Manuscript received November Ii, 2008, accepted for publication November 28, 2008. JALcA, VOL. 104. 2009
  • 2. 170 BRINE CuRING ADDITIVES INTRODUCTION removal efficiency. Finally, the possibility of using SL as brine curing enhancers was investigated. Curing of raw hides and skins with common salt (sodium chloride) is the most popular preservation method used currently. Sprinkling of solid salt on the flesh surface of the EXPERIMENTAL. hide, known as green-salting, is extensively used in warm countries like India. Conversely, most American and Materials European hide processing facilities typically treat their hides Two fresh cow hides were purchased from a local abattoir. in raceways tilled with a highly concentrated solution of They were soaked in 200% water with 0.15% Boron TS sodium chloride (brine). The economics of brine curing of (Rohm & Haas Co.. Spring House. PA) and 0.10% Proxel hides and skins have been affected recently by increasing (Chemtan Co. Inc., Exeter, NH) for 2 h and then fleshed. commodity prices for sodium chloride.' Furthermore, the Approximately 6 x 10 in (15 x 25 cm) pieces were cut and large amount of salt needed creates environmental issues stored at -20 °C. They were thawed at 4 °C just before use. when it is soaked out, contributing to 40% of the total Food grade sodium chloride of minimum purity 99.82% (US dissolved solids generated in the entire process of leather Salt Corporation, Watkins Glen, NY) was used in the brine manufacturing.2 preparation. Three commercial degreasing agents marketed to the leather industry and identified as degreasers 1, 2 and 3, In our previous paper' we developed a mathematical model as well as the experimental sophorolipid (SL) developed in that described the diffusion of sodium chloride into the hide our research facility, were used without further purification. during the curing process. We concluded that the usage of All other chemicals were reagent grade and used as saturated brine as well as a minimum float of 500% yielded received. an optimal diffusion rate. We also proved by means of epifluorescence microscopy that salt diffused into the hide Stratigraphic Study mainly from the flesh side, which presents a less compact Thawed hide was cut into square pieces of approximately 4 structure and greater porosity than the grain and upper x 4 in (10 x 10 cm) with an average weight of approximately corium. However, the fatty or adipose tissue present on the 100 g. They were transferred to a Dose drum (PFI 300-34; flesh side was reported to retard the diffusion of salt into the Dose 131 Maschinenbau GmbH, Lichtenau, Germany) and hide.' Thus, a poor fleshing of the hide prior to the cure may tumbled at 6 rpm in a 500% float of 95 'SAL brine solution further aggravate this phenomenon. (25.1 g NaCl/lOO (y brine) for varying time intervals, after which they were removed from the drum, hand-squeezed to The use of degreasing agents in the leather manufacturing wipe off excess water, split into three layers (flesh, middle process is quite widespread and they are mainly utilized and grain), sealed in plastic bags and stored at 4 °C until during soaking, liming and deliming to decrease the fat analysis. content of the wet blue below the norm value.' However, there is no literature regarding the usage of these degreasers Degreaser Study in the cure. If the use of a degreasing agent along with the Pieces of hides of approximately 100 g were tumbled at 6 brine could accelerate the penetration of salt into the hide, rpm in a 500% float of initially saturated brine (100 'SAL, then turn-around times in the raceways would be reduced 26.4 g NaC1/100 g brine) for 16 h. To the test samples, the and thus additional curing capacity would be created. required volume of degreasers 1, 2 or 3 was added to the brine held in the drum and tumbled for jive minutes to ensure Sophorolipds (SL) are glycolipid surfactants produced in a uniform distribution of the product within the brine. Due large quantities by the yeast Candida bonbico1a. Among to its low solubility, the SL solution was prepared in the their desirable properties, they are biodegradable, non- laboratory by adding the required amount of SL powder to ecotox ic, and non-foaming ,6 Sophorol ipids are currently the saturated brine solution and stirring for at least 24 h, after used in the cosmetic industry and as an active ingredient of which the solution was dumped into the drum. An SL dishwashing detergents. 7 The potential for their use in the solution that had been filtered through a sintered glass funnel leather industry as a degreasing agent is therefore worthy of immediately after 24 h of stirring was also tested. Control consideration. samples to which no degreaser was added were also run for all experiments. The concentration of degreasers or SL was In the present paper we first carried out a stratigraphic study always expressed with respect to the combined weight of to monitor the distribution of sodium chloride and water in a hide and brine. No further salt or brine was added to the hide throughout the curing process. The effect of the cure on drums during the experiments. Brine density was determined the collagen denaturation temperature was also examined. by gravimetric analysis. Hide density was assumed to be Ig! Furthermore, we used scanning electron microscopy in cm3. backscattering electron mode to establish changes in the distribution of sodium chloride within the hide. Next, we evaluated the effect that commercial degreasers exerted on the penetration of salt into the hide, as well as their fat JALCA. VOL. 104, 2009
  • 3. BRINE CURING ADDITIVES 171 Determination of Moisture and Ash Content were processed and analyzed using Fovea 3.0 plug-ins An oval arch punch (C.S. Osborne & Co., Harrison. NJ), 7/8 (Reindeer Graphics, Asheville, NC) for PhotoShop, v. 7 inches (2.2 cm) in diameter, was used to sample the pieces of (Adobe Systems, Inc., San Jose, CA). The montages were hide. Samples were clipped to minimize variability due to spatially filtered with a Gaussian blur (3 pixels) to reduce long hair. Next, they were weighed on an analytical balance local noise and a line profile was drawn in each image into dry tared crucibles and dried in a vacuum oven at 80 °C extending from a point at the grain surface to a point at the for 18 h. After cooling in a desiccator they were weighed flesh surface. The line profiles were then plotted as gray and percentage moisture was calculated. Dry samples were level versus distance (data not shown), and the ranges of gray placed in a muffle furnace and ashed at 600 °C for 2 h. After levels for different curing times were plotted in Figure 3. cooling in a desiccator, they were weighed and percentage ash was calculated. All samples were run at least in Statistical Analysis triplicate. Data were analyzed by analysis of variance followed by a Dunnett's test to compare each treatment (degreasing agent) Determination of Fat Content with the control. Further comparisons were made using In order to accurately compare results among different orthogonal polynomial contrasts to test the linear and samples, fat content' is expressed in terms of moisture and quadratic trends due to degreaser 1 concentration. An ash free basis (MAFB).9 All samples were run in triplicate. orthogonal contrast was also used in the sophorolipid study to determine the significance of the filtering effect. Determination of Thermal Stability Differential scanning calorimetry (DSC) analysis was performed on a Multi-Cell Differential Scanning Calorimeter RESULTS AND DISCUSSION CSC-4 100 (Calorinietry Sciences Corporation, Lindon, UT). An aliquot of raw or cured hide of approximately 100 mg Stratigraphic Study was weighed into a stainless steel pan and placed in the The layer-wise distribution of water and salt (ash) in a hide calorimeter. Another pan containing approximately the cured for various intervals of time was monitored (Figures la same weight of a 5% NaCI solution was used as a reference. and Ib). Typically, the flesh layer included the flesh itself When raw hide samples were analyzed, nanopure water was and the attached adipose tissue; the middle layer represented used as a reference. Both sample and reference capsules the majority of the corium or true skin; and the grain layer were weighed before and after the DSC run in order to included the junction of grain and corium and the epidermis. determine any possible weight loss by leakage. Samples The initial moisture content was highest in the region of the were heated from 10°C to 120°C at 1.5 °C/min. The peak epidermis and decreased toward the center of the corium. maximum temperature was taken as the hide's denaturation Whereas the diminishing moisture content of the flesh layer temperature (T1)). All samples were run in duplicate. leveled off at 54% after 2 h of cure, the moisture content of the middle and grain layers continued to diminish over a Back-scattered/Low Vacuum Scanning Electron 24-h period to less than 45% (Figure la). The salt content of Microscopy (SEM-BSE) a raw hide was found to be less than a 0.5%. As curing Backscattered electrons consist of high-energy electrons progressed, salt content increased in all three strata: the flesh originating in the electron beam that are reflected or layer contained the highest amount of salt at all curing times backscattered out of the specimen interaction volume. The (Figure lb). Noteworthy, the salt content of the flesh layer brightness of the SEM-BSE image tends to increase with the after 30 min and 1 h of cure was 6.7 and 7.1%, respectively, atomic number. Two major advantages over conventional but only 1.6 and 1.9%, respectively, in the grain layer. SEM in the secondary electron image mode are the high- quality atomic number contrast images produced and the These figures demonstrated that salt entered the hide mainly simplicity of the technique, which does not require a from the flesh side, which is in agreement with the findings conductive coating.'' of McLaughlin and Theis." It was also confirmed that the epidermis acted as a semipermeable membrane, which A piece of raw hide of approximately 1 x 1 in (2.5 x 2.5 cm) allowed the withdrawal of water by osmosis but did not was immersed in a beaker containing 500% v/v float of a allow salt to penetrate through it. 12 Thus, whereas water was saturated brine solution and gently agitated for varying extracted from the hide by both sides, only the flesh side was intervals of incubation time. A 2-3 mm wide slice of the susceptible to extensive absorption of salt, which then sample was excised manually with a stainless steel razor diffused into the hide and towards the grain. The porous blade (cutting from flesh surface toward the grain), mounted nature of the hide may have also contributed to the diffusion on aluminum stubs, and then irradiated at an accelerating of salt through the hide by capillarity. voltage of 25 kV in low vacuum mode (spot size 3.0, pressure 0.98 Torr) using a Quanta 200 FEG environmental By means of the equation, scanning electron microscope (FEI Company, Hillsboro, OR). Samples were imaged as montages at a magnification Saturation = (%A>/ . 100 of 50 x . Individual montages of images at each curing time sture ). %Mot ( , '3 -9 JALC4, VOL 104, 2009
  • 4. 172 BRINE CURING ADDITIVES (a) the hide salt saturation levels at various curing times were calculated (Figure lc). O'Flaherty' 3 claimed that a 70% salt saturation of the water remaining in the hide with a maximum 70 -- Flesh layer i. • Midcle layer of 50% moisture was needed for a proper cure. Later on, a Q-) U ---4---- Grain layer new minimum standard of 85% salt saturation was established 60 • by the U.S. Hide, Skin & Leather Association.' 4 The salt £ saturation of the flesh layer was the highest of all three layers 55 -- at all curing times. The reason was found in the rapid U, dehydration experienced in the early stages of the cure along 0 E with the almost exclusive penetration of salt from the flesh a) 45 side of the hide. The differences of hide salt saturation levels 40 among the three layers become less pronounced after 16 h of cure. Although we did not sample the hides beyond the 24 h 35 curing time frame, one could assume that the hide and 0 4 8 12 16 20 24 surrounding brine reached equilibrium after about one day of Time (h) brining. In fact, it was previously reported that a hide continuously brined for 48 h took up moisture as well as salt ;4 ' 5 brining a hide beyond the equilibrium did not necessarily entail a more proper cure. (t) 20 The denaturation or melting temperature (T,) of the grain, middle and flesh layers of a hide cured for various time intervals was monitored (Figure 2). The hide's collagen, 15 upon heating, undergoes a transition from the triple helix to C a randomly coiled form in which the three chains are a-) C separated.' 6 The flesh layer was the first to reach a constant 10 T0 of 78 °C after only 2 h of cure. On the other hand, about 4:: (4, 8 h of cure were needed to level off the temperature curve of f3 the middle and grain layers IT = 82 °C). The increase of the CD -o thermal stability of the hide upon brining could be ascribed to two factors. The first and most important factor is the dehydration of the hide. Kopp et al. 17 developed a mathematical function that showed an exponential decrease ofT0 with increasing moisture content. The second factor is 0 4 8 12 16 20 24 protein salting out and aggregation. The brine, despite the Time (h) disruption of some hydrogen bonds due to the withdrawal of water, induces this phenomenon, which was reported to further stabilize the collagen molecules, thus increasing the (c) values of TD.'8 100 85 U _- 80 C - 80 - - -1 0 de A ' 60 1 75 A . - 40 a - i— U) 70 - ZFlesh layer a) ' 20 Middle layer -- Flesh layer Grain layer 65 I Middle layer - ---.--- Grain layer [I] 60 I I I 0 4 8 12 16 20 24 Time (h) 0 4 8 12 16 20 24 Time (h) Figure 1: Stratigraphic distribution of (a) water (b) ash and (c) hide salt Figure 2: Denaturation temperature (T 1) ) of the grain, middle, and flesh saturation in a hide treated for various intervals of time with a 500% float layers of a hide treated for various intervals of time with a 500% float of an initial 95 'SAL. Each point is the mean of three values, of an initial 95 'SAL brine. Each point is the mean of two values. JALCA, VOL. 104, 2009
  • 5. BRINE CURING ADDITIVES 173 above 200 (16 h), and the higher values were located within the flesh side of the cross-section, with a boundary slowly moving toward the grain side of the cross-section as the hours of curing increased (Figure 3). Degreasing Study The effect of three commercial degreasers on the content of water, salt and extractable fat of the hide after 16 h of brine curing was evaluated (Table I). A degreaser concentration of t.•è 0.5% (w/w) with respect to the combined weight of hide and - - '- I brine was used. Samples that had been brine-cured in the h presence of degreaser I showed a significantly higher salt content than the control, to which no degreaser had been - ,. .. added. Furthermore, degreaser I was shown to be the most efficient as far as its fat-removal capacity, significantly 'J decreasing the extractable fat content with respect to the control. Samples that had been treated with degreasers 2 and 3, despite tending to increase salt content and decrease extractable fat, were not statistically more efficient than the control. The composition of degreasers 2 and 3 was likely the cause of a lower efficiency than degreaser I. Although NLIIi2.tIU: the specific compositions of these commercial products are not disclosed, they are typically composed of a blend of Bck-ttr CT(Cring time in horn) GIK (C.rny Iei rne) nonionic surfactants, modifiers and adjuvants. The Figure 3: Composite images of hide samples, collected at different cur- hydrophilic-lipophilic balance (HLB) is a widely used scale ing times by low vacuum, mixed signal SEM imaging. Image heights in the technology of surfactants; HLB values run from 0 to were adjusted to an average value in order to facilitate comparisons. At 20 and indicate whether a surfactant has greater wetting (low 0 hours (control), the superficial brightness was low and variable in the end of the scale) or emulsifying properties (high end of the lower, flesh side and uniformly brighter in the upper, grain side the scale). It is likely that degreaser I had a slightly higher HLB range of gray levels was narrow, between 69 and 77. At 1-24 hours of than the other two products and hence a higher tendency curing, the average values of brightness were increased almost mono- toward forming oil-in-water emulsions. As a matter of fact, tonically, mainly from the flesh side, but not uniformly some bright the emulsification of fat in water was reported to be a crucial and dark patches were present through 1, 2, 4, 8 and 16 hours. At 24 step for the efficiency of the degreasing process.'9 hours, the brightness was the most uniform, suggesting that the concen- trations of Na and Cl were evenly distributed in the hide. Next, degreaser 1 was selected to study the effect of its concentration on the content of water, salt and extractable fat Cross-sectioned samples of hides, cured up to 24 It duration, of a hide after 16 h of curing with brine (Table II). All three were examined in a scanning electron microscope using a tested concentrations of degreaser (0.25, 0.5 and I% w/w) backscatter detector at low vacuum. Although the backscatter significantly defatted the hide. Furthermore, hides treated signal is not specific for sodium chloride, results of with a concentration of 0.5% also had significantly higher backscattered intensity variations were expected to reveal salt and salt saturation values. The statistical analysis general trends related to diffusion of the dissolved salt that showed evidence of a significant quadratic trend with could be further explored and mapped by energy dispersive increasing concentration of degreaser 1, with a maximum x-ray microanalysis. occurring at a critical concentration between 0.5% and 1%. The usage of a concentration larger than this critical point The range of intensity in backscattered images was adjusted neither further increased the uptake of salt nor additionally to maximize the dynamic range of the detector by adjusting decreased the fat content. That could be ascribed to the fact contrast and brightness values with the waveform monitor that the concentration of surfactants in degreaser 1 was well using the 24-h cured sample. Then images of all the cured above the critical micelle concentration. samples were collected under the same conditions. Line profiles drawn on images front grain side to flesh side of The feasibility of using a sophorolipid (SL; a fermentation an uncured hide (0 h) had a narrow range of low brightness product, under investigation at this location) as a degreasing values (69-77) relative to the values set for the 24-h sample. agent for raw hides was examined. Due to the low solubility At 0 h, higher values were located in the lower half or flesh- of SL in the brine, the effect of filtering the SL solution prior side of the hide. Similar line profiles drawn on backscatter to its use was also examined. By doing this, we ensured that images of cured hides indicated that the range of intensities the brine solution contained the maximum amount of soluble increased monotonically w'th longer curing times, with SL. Hide samples cured with the unfiltered brine-SL solution brightness values extending from a low around 20 to a high displayed significantly higher values of salt and salt saturation /AICA, VOL 104, 2009
  • 6. 174 BRINE CURING ADDITIVES TABLE I Effect of Commercial Degreasers on Brine Curing 10.5% w/wI Treatment Moisture (%) Salt (%) Hide salt saturation(%) Fat (%, MAFB) Control 46.5 + 1.5 11.8 ± 0.9 70.9 ± 7.0 11.8 ± 2.6 Degreaser 1 47.9 ± 3.0 12.9 ± 0.9* 75.2 ± 1.1 7.3 + 0.6 Degreaser 2 46.5 ± 1.0 12.1 ± 0.8 72.1 ± 4.1 8.8 ± 3.6 Degreaser 3 46.7 + 1.7 12.2 ± 0.4 73.1 ± 4.1 8.8 ± 2.2 Average of 8 values Values with * are significantly different from the control (Dunnett's test, p<0.05) TABLE H Effect of Degreaser 1 on Brine Curing Treatment Moisture (%) Salt (%) Hide salt saturation (%) Fat (%, MAFB) Control 53.4 ± 2.0 15,2 ± 0.6 79.5 ± 1.3 16.8 ± 2.2 Degreaser 1 [0.25%] 50.4 ± 2.0 13.8 ± 1.1 76.3 + 3.5 7.4 ± 2.4 Degreaser 1 [0.5%] 57.2 ± 4.2 17.1 ± 1.7* 83.5 ± 2.7* 3.8 + 0.9* Degreaser 1 [1%] 56.4 ± 2.9 16.5 + 0.7 81.7 ± 1.9 9.7 ± 2,9* Average of 6 values Values with * are significantly different from the control (Dunnett's test, p<0.05) TABLE LII Effect of Sophorolipid on Brine Curing Treatment Moisture (%) Salt (%) Hide salt saturation (%) Fat (%, MAFB) Control 45.0± 1.4 11.8+0.6 72.8± 1.5 15.3 ± 0.5 SL Non-filtered 46.6 ± 0.8 12.5 ± 0.3* 74.9 + 0.8* 9.1 ± 2.3* SL filtered 49.7± 1 . 6* 13.0±0.5* 73.0± 1.1 11.1 ± 1.9* Average of 5 values Values with * are significantly different from the control (Dunnett's test, p<0.05) JALCA, VOL. 104, 2009
  • 7. BRINE CURING ADD[ FIVES 175 than the control (Table Ill). The extractable fat was also findings were corroborated by the pictures taken with a significantly lower than the control. When a filtered brine- scanning electron microscope run in the back-scattered SL was used, the values for moisture, salt, and extractable fat electron mode. Furthermore, the thermal stability of the hide content were significantly different from those of the control. increased upon curing, mainly due to the simultaneous Hence, SLs were demonstrated to have a degreasing activity dehydration and salting out processes of the constituent on the hide. The percentage of fat removed from the hide collagen. If 0.5% (w/w) of a commercial degreaser, made of was 40.5 and 27.5% for the unfiltered and filtered SL-brine a blend of nonionic surfactants, had been added to the brine, solution, respectively. These figures are similar to those the fat content of that hide was significantly decreased and obtained for the commercial degreasers (from 25.4% for the uptake of salt was also significantly enhanced. Since degreasers 2 and 3 to an average of 53.4% for degreaser 1). another two commercial degreasers exhibited less stimulation The undissolved SL likely provided a reservoir of active of salt uptake, we concltided that the composition of the surfactant as the initial concentration of solubilized SL degreaser was a critical parameter for this specific purpose. suffered from dilution or inactivation. The sophorolipid tested showed remarkable degreasing properties and enhanced the uptake of salt by the hide if it From Tables I, II and III it can be seen that test samples with was used above the solubility limit. These facts along with a significantly higher amount of salt than the controls also its low-foam properties and low cost (from $1 to 3/kg;22) exhibited a significantly lower fat content. However, this make it an attractive choice of surfactant. One may statement was not verified in the other direction. It was also hypothesize that the addition of small amounts of a proteolytic observed that a significant effect of the degreaser on the enzyme along with a degreasing agent would enhance the fat content of salt and fat did not necessarily entail a significant removal action, since it would facilitate the breakdown of the increase in the salt saturation levels. That could be attributed proteinaceous membrane of the fat-containing sac .21 to the wetting properties of the degreasers, which did not Nevertheless, the detrimental effect that this treatment could significantly alter the amount of remaining moisture in the have on the grain is an important drawback. hide after the 16 h curing time frame (Tables I and 11). In this paper, we gave an overview of the brine curing It is important to bear in mind that the results presented in process of raw hides and also suggested the use of an additive this study are based on the analysis run on different areas of (e.g., commercial degreasers, sophorolipid) to enhance the two cow hides. Variance in the results can be attributed to uptake of salt and remove a major amount of the fat. It is some extent to the variability always found in biological important to note that actual raceways or vats are operated material. III although the hides were washed, continuously. Thus, it will be essential to find a way to fleshed, cut up and stored in the freezer on the same day that remove the fat that builds up in the vat. the animal was slaughtered, some damage to the hide due to a delayed cure might have taken place. A delayed cure of only a few hours was reported to slow down the diffusion of ACKNOWLEDGEMENTS salt during the early stages of the cure' Furthermore, and for the particular case of fat content, some variability could The authors appreciate the assistance of the following: Dr. be attributed to the horizontal distribution of grease, which is Richard Ashby, Guoping Bao, Dr. Eleanor Brown, Nicholas more abundant in the looser and more flexible areas (e.g., Latona, Joe Lee, Dr. Justin Martin, Paul Pierlott, Dr. Daniel belly; 20). Despite all these facts, the coefficients of variation Solaiman, Maryann Taylor and Amanda Tiscavitch. (CV) obtained for the determination of moisture, salt and salt saturation were 3.97, 5.76 and 3.54%, respectively, which indicate good precision." In the particular case of the REFERENCES determination of extractable fat, a CV of 21.3% was relatively precise, considering the low analytical values of I. Personal communication, Ed Godsalve, WE CO., 1991, that parameter. Inc., 2006. 2. Rajamani, S. Cleaner tanning technologies in the beam house operation. UNEDO report. pp. 9-18, 1998, CONCLUSIONS 3. Hernàndez Balada, E.; Marmer, W.N.; KolomaznIk, K.; The purpose of research reported in this article was to Cooke, P.H.; Dudley, R.L. Mathematical model of raw evaluate the possibility of using degreasers as brine curing hide curing with brine. JALCA 103, 128-134, 2008. additives, with the aim of enhancing the uptake of salt by the 4. Stuart, L.S.; Frey, R.W. Effect of adipose tissue fat on the hide. In the stratigraphic study carried out in order to get a green-salting of heavy hides. JALCA 35, 414-418, 1940. better understanding of the curing process, we found that the 5. Stockman, GB.; Rangarajan, R.; Didato, D.T. The epidermis acted as a semipermeable membrane, enabling the replacement of nonylphenolethoxylates (NPEs) as diffusion of water from the hide and into the surrounding degreasing agents in wet blue manufacture. World Leather, float as well as hindering the diffusion of salt into the hide, October 2005. which occurred from the flesh side overwhelmingly. These 6. Garcia, R.A.; Solaiman, D.K.Y. Government scientists find new uses for rendered products. Render, June 2008. JALcA, VOL. 104, 2009
  • 8. 176 BRINE CURING ADDITIVES 7. Solainian, D. K. Y. Applications of microbial biosurfactants. 17. Kopp, J.: Bonnet, M.; Renou, J.P. Effect of collagen Inft.rm 16, 408-410, 2005. crosslinking on collagen-water interactions (a DSC 8. Taylor, M.M.: Diefendorf, E.J.; Phillips, J.G.: Feairheller, investigation). Matrix 9, 443-450, 1989. S. H.; Bailey, D.G. Wet process technology 1. Determination 18. Komsa-Penkova, R.; Koynova, R.; Kostov, G.; Tenchov, of precision for various analytical procedures. JALCA 81, B.G. Thermal stability of calf skirt collagen type I in salt 4-18, 1986. solutions. Biochim. Biophvs. Acta Protein Siruct. Mo!. 9. Donmez, K.; Kallenberger, W.E. Total crude fat Envmol. 1297, 171-181, 1996. determination in hides. JALCA 89. 369-390, 1994. 19. Thanikaivelan, P.; Rao, JR.; Nair, RU.: Rarnasarni, T. 10. Robinson. B.R.; Nickel, E.H. A useful new technique for Progress and recent trends in biotechnological methods mineralogy: the backscattered-electron/low vacuum for leather processing. Trends Thotechnol. 22. 181-188, mode of SEM operation. Am. Mineral. 64, 1322-1328, 2004. 1979. 20. Balderston, L. The distribution of grease in leather. 11. McLaughlin, G.D.; Theis, E.R. Science of hide curing. JALCA 17, 405-407, 1922. JALCA 17, 376-399, 1922. 21. Taylor, M.M.; Diefendorf, E.J.; Artymyshyn, B.: 12. Tancous, J.J. A study of a drawn condition, caused Hannigan, MV.; Phillips, J.G.; Feairhcller, S.H.; Bailey, through osmosis, encountered in some brine-cured hides. D.G. The chemical and physical analysis of contemporary JALCA 58, 143-154, 1963. thru-blue tanning technology, 1984. Animal Biomaterials 13. O'Flaherty, F. Curing study part 1: Moisture to ash Laboratory, ERRC, Philadelphia, PA 19038. Available relationship. Leather and Shoes 138, 31-34, 1959. from senior author at maryann.taylor@ars.usda.gov . 14. Trade Practices for Proper Packer Cattlehide Delivery, 22. Sun, X.X.; Choi, J.K.; Kim, E.K. A preliminary study on 3' ed., Leather Industries of America and U.S. Hide, the mechanism of harmful algal bloom mitigation by use Skin & Leather Association, pp. 12-19, 1993. of sophorolipid treatment. J. Exp. Mar. Biol. Ecol. 304, 15. Strandine, E.J.; DeBeukelaer, F.L.; Werner, G.A. 35-49, 2004. Stratigraphic distribution of sodium chloride and water 23. Langridge, D.A.; Long, A.J.; Addy, V.L. The impact of in fresh and brined steer hide. JALCA 46, 19-34, 1951. sebaceous grease on the leather industry. JALCA 101, 16. Miles, CA.; Bailey, A.J. Thermal denaturation of 45-50, 2006. collagen revisited. Proc. Indian Acad. Sci. (Chem. Sci.) 111, 71-80, 1999. JALcA, VOL. 104, 2009