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Vallini*,
A.
revised
and Franca
Perghem‡
May 1989
)
The
disposal problem represented by vegetable-tannery sludge is of great and everincreasing concern in Italy. Such sludge is of a highly polluting nature and therefore,
requires a reliable and safe treatment to make it harmless before release into the
environment. Vegetable-tannery sludge contains some very toxic compounds, mainly
polyphenols (i.e. tannins) and sulphides, that are hazardous to biological systems.
This paper deals with experiments evaluating the feasibility of vegetable-tannery
sludge management and recycling by an integrated composting process. Static
windrow technique with forced air and temperature feedback has been adopted for
composting a mixture of vegetable-tannery sludge and organic biodegradable fraction of municipal solid waste (MSW) as bulking agent. Physico-chemical, microbiological and phytotoxicological aspects of this compost production from vegetabletannery sludge are here emphasized along with some technological details.
Key Words-Composting, tannery sludges, municipal solid waste (MSW), temperature feedback control, forced air aeration, tannin reduction, sulphide
removal.
1. Introduction
The two main tanning methods, vegetable tannage and chemical tannage produce wastes
which differ widely in physical, chemical, toxicological and microbiological characteristics.
Tannage with natural vegetable bark extracts is the principal tanning method for the
production of sole leather (hard leather) while tanning with chromium salts is used to
obtain light, smooth and soft leather suitable for manufacturing goods such as shoe
uppers, handbags, gloves and a variety of clothes.
Although various treatment procedures for disposing tannery by-products have been
suggested, sludge from tannery wastewater depuration is still an environmental problem.
This paper explores the possibility of recycling vegetable-tannery sludge into a soil
conditioner by using careful composting techniques. The objective of this process is to
eliminate pollution, crop contamination and health hazards.
The present study on this specific tannery waste arose from the fact that, until now,
among all tannery by-products, sludges from tannery wastewater treatment have been
considered as undesirable pollutants. See however Giugliano & Paggi (1985).
The main concern of recycling vegetable-tannery sludge into an organic soil conditioner is its high concentration of toxic compounds. In particular, vegetable-tannery
sludge derived from the physico-chemical treatment of process wastewaters is extremely
*
CNR, Soil Microbiology Center, Via del Borghetto 80, 56100 Pisa, Italy.
†Department of Environmental Sciences, University of Venice, Venice, Italy.
‡Department of Chemistry, University of Florence, Florence, and Luigi Sacconi Center,
sullArno, Italy.
Santa Croce
278
in color, and still contains considerable quantities of tannins and their phenolic
derivatives. Sulphides and other reduced sulphur compounds are also present. Tannins
and phenolic derivatives play a key role in promoting phytotoxicity and allelopathy
phenomena in soil (Wang et al., 1967; Whittaker & Feeney, 1971; Rice, 1974; Chou &
Young, 1975; Swain, 1979). Sulphides result from the lime-sulphide treatment of hides,
which dissolves unwanted skin and loosens hair during the preliminary phases of
tanning. Besides showing a strong direct toxicity on vegetable tissues, the soluble
fraction of reduced sulphur compounds, principally hydrogen sulphide and mercaptans,
has proved to inhibit nitrification in agricultural soils (Bremner & Bundy, 1974).
Eliminating toxicity associated with tannins and reduced sulphur compounds and
recycling vegetable-tannery sludge into a soil conditioner can be achieved by sustained
high rate aerobic (oxidative) microbial activity. It is common knowledge that tannins are
recalcitrant to microbial degradation although it does occur slowly in aerobic conditions
(Lewis & Starkey, 1968). Moreover an aerobic environment associated with temperatures around 60C enhances the fast oxidation of sulphides to sulphates. These
conditions occur in some composting piles governed according to a deliberate process
based on the Rutgers strategy (Finstein et al., 1980) as described in this paper.
high
Sludge used during composting experiments came from wastewater treatment facilities
of a vegetable tannery located in the municipal district of Castelfranco di Sotto (Pisa),
right in the heart of the area of Tuscany called &dquo;Leather Country&dquo; because of its high
density of factories for tanning hides.
Sludge was drawn from the storage-sedimentation tank, downstream of the physicochemical step of the treatment undergone by all tannage wastewaters. Table 1 shows
analyses of a sample of the vegetable-tannery sludge.
2.2 Source and characteristics
Because of its high fluidity, vegetable-tannery sludge was mixed with a bulking material
so that it could be shoveled for arranging stable windrows compatible with composting
as regards moisture and porosity.
Since one of the aims of this research was to investigate the viability of combining
vegetable-tannery sludge and biodegradable organic fraction of solid urban waste
(BOFSUW) in the composting process, the latter was chosen as bulking agent. It was
provided by the Dano facilities operating in Pistoia. Table 1 shows analyses of a sample
of the BOFSUW.
2.3
Sludge and BOFSUW were mixed in the ratio of 35% to 65% (w/w), approximately 12%
and 88% dry-matter contributions respectively, giving a mixture (Table 1) with a
moisture content such as to allow the right evolution of biological reactions during the
whole composting process without additional water.
The mixture was formed into 1.8 m high windrows of about 21.8 metric tons each.
Forced air was blown in from the bottom (Fig. 1). For process control, a modification of
the classic Rutgers strategy (MacGregor et al., 1981; Finstein et al., 1983) was adopted.
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279
TABLE 1
Physico-chemical characteristics
of: A, A
Organic carbon x 1.724; tH2S and HS ; $ As total phenols; This high value of moisture content must
be interpreted as consequence of a heavy rainfall during transportation of the BOFSUW from the Dano
plant in Pistoia to the experimental yards in Pisa by an open truck.
1. Scheme of a composting windrow with a forced aeration system blowing air from the bottom.
125 mm perforated flexible plastic pipe; (2) Blower; (3) Blower control board; (4) Thermostat set on 55C;
Holder for temperature sensor and 02 meterprobe.
Fig.
(1)
(5)
280
The use of an 02 feedback control system was integrated with the basic temperature
feedback control by forced-pressure ventilation embodied in the Rutgers strategy. The
arrangement for the blower operation in each windrow was as follows: a temperature
controller unit was connected with a temperature sensor placed in the pile. When
temperature at the sensor reached 55C, the blower worked continuously. At temperatures lower than 55C, the blower was controlled by a molecular oxygen meter
(Microprocessor Based Universal Oxygen Indicator, Model 2609, Orbisphere Laboratories, Geneva, Switzerland). The oxygen meter probe was placed in the center of the
pile. Whenever the oxygen concentration in the inner atmosphere dropped below 10%
the blower went on. When the temperature was below 55C and the 02 concentration
exceeded 10% the blower operated on a timer. The time-controlled blower operation for
the first 52 hr was 1.5 min of forced aeration every 15 min. From 400 to 504 hours the
blower was on for 1 min every half hour. The timer was then disconnected. A one-fourth
hp, 16.5 cm radial blade blower, 2500 r.p.m., with an air flow delivery of 605 m3hr- was
used for each windrow.
2.4
Temperatures were measured by a four-channel pyrometer connected to four thermocouples sited at different depths in each windrow: at 10, 30, 90 and 170 cm from the
upper surface. The pyrometers recorder registered impulses from each thermocouple
every 3.5 min giving four differently coloured dotted traces. Samples for physicochemical, microbiological and phytotoxicity analyses were prepared as follows: 15
separate 0.5 kg samples were taken from five different layers in the piles (three
respectively from different locations on the upper surface, at 10, 30, 90 and 170 cm in the
pile). Samples were then mixed together to obtain a single sample representative of the
composting material.
In order to determine moisture content, a 100 g sample was placed in a porcelain dish
and heated in an oven at 105C, until constant weight was reached.
Sludge pH was measured by electrometric determination following the procedures
reported in the 13th Edition of &dquo;Standard Methods&dquo; (APHA, AWWA, WPCF, 1971)
while the pH of solid samples (BOFSUW, starting mixture and compost) was determined following the method suggested by Lotti & Galoppini (1980) for soil analysis: 40 g
of the material were placed in a beaker containing 100 ml of distilled water; the
suspension was stirred for at least 30 min. and the pH measured by a glass electrode.
Ash content was determined by igniting dried samples at 750C for four hours
(Riffaldi et al., 1983).
Total organic carbon in the raw materials and compost was determined by the
potassium dichromate oxidation method. The humified fraction of total organic matter
(total organic carbon x 1.724) was analysed by the acetyl-bromide procedure described
by Springer (1928).
Total nitrogen content was determined by the Kjeldahl procedure. Determination of
NH4 - N and (N03 + NOz ) - N were made by using the steam distillation method of
Bremner & Keeney (1965). Organic nitrogen was calculated by subtracting NH4 -N
and (N03 + N02 N from total N.
Total phosphorus was measured by absorption at 430 nm of the phospho-vanadomolybdate complex and total potassium was determined by flame photometry directly on
,
281
For total sulphides (dissolved H2S and HS-) the titrimetric (K-iodine) method was
used following &dquo;Standard Methods&dquo; (APHA, AWWA, WPCF, 1971).
Cu, Zn, Cd, and Pb were determined by flame atomic absorption spectrophotometry
and Ni and Cr by graphite furnace atomic absorption spectrophotometry.
Folin-Danis reagents were used for determinations of tannins as suggested by AOAC
(1970).
Counts of the total number of aerobic bacteria, actinomycetes and fungi and analyses
of the aerobic cellulolytic bacteria and ammonia producing bacteria followed the
techniques described by Pochon & Tardieux (1962). Enumeration of autotrophic
nitrifying bacteria by most probable number (MPN) was made according to the methods
reported by Schmidt and Belser (1982). Cellulolytic and ligninolytic fungi were counted
following the procedures suggested by Hudson (1972) and Eggins (1964).
Fecal coliforms and streptococci and Salmonella sp. were isolated as previously
suggested by de Bertoldi et al. (1985a).
Physico-chemical parameters
3.1.1 Temperature
Temperature measurements taken at different depths in the windrows showed that the
thermophilic step of composting (T > 45C) was completed within 21 days from the start
of the process (Fig. 2). This result was made possible through the use of a forced pressure
ventilation system, actuated via temperature feedback control. In fact the highest
temperatures fluctuated around 60C (max: 62.6C) allowing for high microbial metabolic activity and increased oxidation of organic matter. The collapse of the microbial
community brought on by excessive high temperature was avoided contrary to what
would have happened in forced aeration windrows without temperature control.
Without thermal control, temperatures of over 70C which are lethal to most microorganisms could be maintained for a few days. By avoiding this overheating a
was
obtained.
3.1.2 Moisture
During composting, the moisture content of the windrows decreased from 77.9 to 39.2%
within only thirty days (Fig. 3). The main mechanism of water removal was vaporization
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282
into the blower air as it was heated by microbial activity. Vaporization of water removes
heat and lowers the temperature (Miller & Finstein, 1985; Finstein et al., 1986). On the
other hand, ventilative heat removal in metabolically active composting piles allowed
progressive drying of the initial substrate biomass. Since heat generation meant
degradative biological activity, the course of drying during composting was used as an
indicator of organic matter decomposition and process performance (Fig. 3) (Finstein et
al., 1983).
3.1.3
Oxygen concentration
Throughout the process the 02 level in the piles interstitial atmosphere dropped below
10% intermittently only from 52 to 57 hr actuating blower operation via 02 feedback
control (Fig. 4). This slight and transient scarcity of molecular oxygen took place
immediately before the blower operation was by temperature feedback control alone,
i.e., from 57 to 400 hr, with peaking temperatures of over 55C. Altogether the 0,
feedback operated as an override control only for 1.7 hr. Anyway during composting 02
concentration in the intestitial gases ranged from 9.5 to 21 % with a median of 18.7%.
Therefore piles were well oxygenated throughout.
3.1.4 Air flow and balance of materials
The air usage was 7834 m3 per initial (wet) metric ton over the first 21 days, equivalent to
a mean of 15.5 m3 ton- hr-. Because of the 02 feedback control, blower operation time
peaked to 100% from 52 to 57 hr for a short period while 100% blower duration was
42.3% on the whole time during the temperature feedback control period. This testifies
that temperature feedback control seems clearly to prevail over the 02 feedback control
in affecting this managed composting process.
3.1.5 pH
The mixture of BOFSUW and vegetable-tannery sludge had an initial pH value of 6.0
falling within the optimal range of pHs (5.5 to 8.0) (de Bertoldi et al., 1982a). A
substantial increase of the pH during the thermophilic step of the process (Fig. 2) was
due to the intense proteolytic microbial activity producing ammonia (de Bertoldi et al.,
1983a, 1983b). Stabilized compost showed a nearly neutral pH of 7.1 (Table 2) which is
compatible with agronomical uses.
BOFSUW +
vegetable-tannery sludge. 0 ,
283
Fig.
Fig.
4. a, blower
vegetable-tannery sludge
mixture
during composting.
284
285
3.2 Dynamics
286
Fig. 5. Dynamics of nitrogen in its different chemical forms and counts of the autotrophic nitrifying bacteria
during the composting of BOFSUW + vegetable-tannery sludge. 0, 10 cm; , 30 cm; * , 90 cm; ~ , 170 cm.
nitrification is very slow, if not completely inhibited, above 40C and at high concentrations of ammonia (Alexander, 1971; Loher, 1974; Focht & Chang, 1975).
3.3 Control
of pathogens
Phytotoxicity analysis
The highest levels of phytotoxicity were found in aqueous extracts during early stages of
the process (Fig. 6). The substrate lost its phytotoxic effect within fifteen days after
composting had begun. Such an evolution of the phytotoxicity can be explained
assuming that the organic composting material during the thermophilic phase accumulated a large quantity of microbial intermediate metabolites which normally show a
strong allelopathic effect on plant physiology. Later the toxic intermediate metabolites
were stabilized through humification. (Zucconi et al., 1981 a; 1981 b).
Moreover because of their soluble nature hydrolyzable tannins represent the phenolic
Downloaded from wmr.sagepub.com at ISWA Member Access on May 25, 2015
287
Fig. 6. Phytotoxicity pattern during composting of the BOFSUW + vegetable-tannery sludge mixture.
Germination tests were carried out on Lepidium .sativum (cress) seeds treated with the 10% dilution of the
aqueous extract from the mixture whose actual moisture content was corrected to 60% before testing.
Germination index was obtained by application of the following equation:
G
G,
where
xL
R XxL-L,
a
=
100,
R, and R, are respectively the number of seeds germinated on control Petri dishes and on treated plates,
while L, and L, are root lengths of germinated seeds in control and extract-added dishes respectively.
fraction of vegetable tannery sludge most likely to exert phytotoxicity (Wang et al., 1967;
Vallini et al., 1984).
The intense metabolic activity of ligninolytic fungi during composting suggested that
this method of tannery sludge treatment could be suitable for eliminating or greatly
reducing phytotoxicity due to the phenolic soluble fraction of the sludge itself.
The
tanning industry plays an important role in the Italian national budget (Simoncini,
1982). However, in Italy as well as in other countries tanning industry represents one of
the manifacturing fields heavily involved in freshwater and soil pollution because of the
highly toxic nature of wastewater coming from hide processing.
The present work has been an evaluation of a composting technique applied to the
of vegetable-tannery
288
for agricultural uses, (c) reducing the total costs of vegetable-tannery effluent treatment
and disposal by recovering of the fertilizer value from the sludge. It clearly appears that
all these objects have been attained.
Compost derived from our experiments showed physico-chemical, biological and
organoleptic characteristics compatible with organic fertilizers for crops. The 42%
content in organic matter (on a dry-matter basis) of which 33.19% (g/d.w.) was humified
and the total nitrogen of 1.84% (g/d.w.) giving a 13.2 C/N ratio made a compost that is
balanced in fertility factors. The near-neutral pH (7.1), the low moisture content (39.2%)
suitable for transportation and spreading on the fields, together with the presence of a
higher number of micro-organisms involved in soil fertility-not to mention nil
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to
the
Scientific
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