The Science of the Total Environment, 81/82 (1989) 521-542 521

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

COMPOSTED MATERIALS AS ORGANIC FERTILIZERS

N. SENESI

Istituto di Chimica Agraria, Universit~ di Bari, Via Amendola n. 165/A,

70126 Bari (Italy)

SUMMARY
The subject-matter of this review paper is divided into three sections. The
first section briefly discusses on input, transformation and loss of native and
added organic matter in soil and on principal effects of fresh organic matter
addition on soil properties. The subject of the second section focuses on organic
waste composting process, substrate materials and products of compostation, i.e.
composts. The third section discusses extensively on the most commonly used
criteria and parameters for the evaluation of compost quality as organic
fertilizers, including various proposed "humification degree" indexes and compos-
itional, structural and functional properties of humic-like substances in
compost. The paper ends with some conclusive comments and recommendations.

INTRODUCTION

Soil organic fertility is unanimously attributed to the multiple and complex

functions exerted by organic components in soil. Organic matter (o.m.) is univer-

sally recognized to highly contribute to maintain the global fertility status and

productivity of soil by governing most physical, chemical, nutritional and biol-

ogical equilibria and processes in the soil-plant system. Organic matter, there-

fore, besides ensuring a balanced growth of plants and soil organisms, garantees

soil conservation and protection towards external factors of disturb and

contamination.

Although the natural sources of o.m. in soil are indigenous plant and animal

debris, cropping wastes and animal manures have been used traditionally as the

only means of maintaining and increasing soil fertility and crop production,

until they have been replaced almost completely by the introduction and extended

use of chemical fertilizers in modern and intensive agriculture. A renewed

interest is growing,however, in the proper recyclation in agriculture of organic

residues from a great variety of natural sources and human activities, in order

to restore organic fertility in organic-depleted soils, to maintain it in intens-

ively cropped soils, and to enhance fertility of intrinsically organic-poor soils

0048-9697/89/$03.50 © 1989 Elsevier Science Publishers B.V.

522

Soil application of organic wastes generally is preceded by treatmens having the

aim of lowering or eliminating possible negative effects and hazards that raw

materials may have on soil properties and organisms.

Composting process is generally indicated as the most adequate pre-treatment

in order to obtain a composted material which may respond more efficiently and

safely than the raw material to soil organic fertility requirements. However, the

characterization of composted materials is still quite vague and no uniformity

exists on what properties should be tested and graded for the evaluation and

specification of the quality of composts as organic fertilizer.

Among the various and numerous quality criteria and parameters proposed, the

degree of humification achieved in the final product of composting, i.e. the

compost, is almost unanimously considered as the most reliable parameter to est-

imate its organic fertilizer value. A number of indexes have been suggested for

the evaluation of humification level during the composting process and in final

compost, but none of them appear to be fully adequate. The characterization of

humic-like products in compost, also in comparison to native soil humic substance

properties, based on the use of introspective, physico-chemical techniques seems

the most appropriate for a correct evaluation of the humic character of the

organic material in compost and its value as organic fertilizer.

NATIVE SOIL ORGANIC MATTER AND ORGANIC ADDITIVES

Input, transformation and loss

The natural sources of o.m. in soil are organic, mostly plant, residues which

are subjected to decay in several, mainly microbially-controlled stages of decom-

position, utilization and transformation leading to more refractory organic sub-

stances. In the initial phase, readily decomposable organic compounds, such as

sugars, starchs, hemicelluloses and aminoacids, and some of the more resistant

materials, such as cellulose, are rapidly decomposed with production of CO 2 and

other volatile compounds, organic acids and other incompletely oxidized compounds

This is followed by a stage in which organic intermediates and newly formed bio-

mass tissues are utilized together with the remainder of cellulose and part of

the lignin, with production of new biomass and further loss of C as CO 2. The

final stage is characterized by a gradual decomposition of more resistant plant

components, such as lignin, and the formation on newly synthesized, more stable

products, the humic substances (HS), which may persist for thousand of years.
 523,

Fertility functions

It is likely that the main contribution of o.m. to soil fertility and plant

growth is indirect and consists in improving a wide number of physical, chemical,

nutritional and biological properties of the soil (1). Most of the beneficial

effects can be attributed to the humus fractions belonging either to recognizable

classes of chemical compounds, i.e. non humic substances, such as polysaccharide~

polypeptides, altered lignins, lipids, etc., or to the newly synthesized, colloi-

dal, polymeric humic substances. In addition, a direct stimulating or inhibiting

action on plant growth has been ascertained for some simple components of soil

o.m., such as vitamins, auxins, aliphatic and aromatic acids, etc.

Effects of fresh organic matter addition

At any given time and condition, a dynamic equilibrium state characterizes the

biological activity and the o.m. evolution level in any soil. This situation can

be altered to various extent by fresh addition of organic materials of different

nature and origin, with beneficial or adverse effects on soil organic fertility.

The introduction of organic substances into the soil, regardless of their

origin, causes an initial variation of both the content and quality of total o.m.

present in the system with the immediate effect of modifying all physical and

chemical equilibria and reactions and microbial processes in which native soil

o.m. is typically involved. Although the amount and composition of added o.m. are

undoubtly the decisive factors which influence the modifications occurring in the

soil status soon after the addition, the initial effects will generally decrease

with time and the system will tend to reach, more or less rapidly, new steady-

state conditions which will be different with respect to those existing before

the o.m. addition. The entity and persistence of the effects largely depend on

the persistence of added o.m. in the soil which depends, in turn, on how much of

the o.m. is resistant to degradation and is incorporated into the native soil

o.m. and how much is mineralized~

Organic C may arrive into the soil in the form of either fresh, undecomposed

wastes, or partially-decomposed/transformed materials, or "well" decomposed mat-

erials, in an a d v a n c e d s t a t e of transformation and stabilization, e.g. composted.

A vaste number of data available in the literature indicate that organic additive

of the first two classes generally exert more adverse than beneficial effects on

soil organic fertility by a number of deleterious modifications of one or more

524

physical, chemical or biological soil properties, while the addition of stabiliz-

ed, partly humified materials seems to affect soil properties beneficially.

An important effect of addition of easily decomposable organic residues to

soil is the modification of its normal biological activity at equilibrium and

broadening the spectrum of soil microbial activity. This results in the immediate

increase of the metabolism of the soil biomass with the production of enzymes

able not only to degrade the added residues, but also to attack the native soil

o.m. at equilibrium. This effect results in a change of the decomposition rate of

native soil o.m. measured in terms of CO evolution and is referred to as the

2
"priming action" (I).

The availability of nutrients such as N, P and S of an organic waste is clos-

ely related to its maturity. A stabilized organic material, well balanced in

nutrients, i.e. with low C/N, C/P and C/S ratios, will support slow rate of

nutrient release, while fresh, labile materials, where these rates are high will

cause a limitation of growth of microbial population which will, therefore,

retard or even stop decomposition and transformation (2), unless N is utilized

from another source in the system. The microorganisms will thus compete with

higher plants for available N in the soil and N deficiency will occur for plants.

Anaerobic conditions may be induced in soils, with a lack of oxygen in the

rhizosphere, by mineralization of large amounts of non-stabilized organic C with

extended 02-consumption and C02-production. If the oxigen supply is insufficient,

soil microorganisms are forced to utilize progressively weaker electron acceptors

~ --
(oxidants), such as NO , MnO 2, FeOOH, SO 4 , H +. These conditions can result in

increased denitrification, reduced nitrification, N-mineralization, and formation

of phytotoxic compounds such as NO2, H2S, CH4 and C2H2 (3).

Application of stabilized organic additives generally have a favourable effect

in increasing the pH-buffering capacity of soil, while application of not well-

stabilized organic materials may result in alterations of soil pH, with benefic-

ial or adverse effects in dependence on the natural soil pH (3).

Seed germination can be inhibited and root elongation depressed for various

crops by addition of immature compost to soil, probably by production of high

amounts of ammonia and ethylene oxide, increased temperature, decreased available

oxygen, heavy metal additions and other effects (4). No negative effect appears,

however, if the doses used are low or a mature, stabilized compost is used (4).

Other undesirable effects related to the use of non stabilized, immature

 828

organic materials may occur, including the addition and/or production in the soil

of low molecular weight acids toxic to plants and microorganisms, phytotoxins and

other organic compounds at phytotoxic levels, allelopathic chemicals, plant and

animal pathogens, soluble salts, toxic heavy metals and, finally, of certain

beneficial micronutrients which may be raised to toxic levels for organisms.

The organic matter effect on crop yield

Application of organic fertilizers has the potential of increasing plant yield

to an extent above that resulting from the application of equivalent nutrients by

inorganic fertilizers. This effect is known as the "organic matter" effect, i.e.

an increase in soil productivity which cannot be explained by mineral nutrient

supply alone, that is by the direct, short-term "fertilizer effect". Data have

accumulated indicating that application of composted manures may result either in

a more efficient nutrient utilization, i.e. a higher nutrient availability and

steeper crop-yield response curve, but with a saturation value yet the same as

that obtained for the inorganic fertilizer application, or even in effects above

those of simple nutrient applications. This suggests a contribution to plant

growth through mechanisms other than simple nutrient supply, and correspond to a

completely different response curve with a higher saturation value (5). An addit-

ional potential effect of o.m. addition to soil on the crop yield curve is the

prevention of the yield reduction observed with excessive amounts of fertilizers.

Irreproducibility is a typical feature of the actual use of organic fertiliz-

ers. In some cases, an evident increase is observed in soil fertility and crop

yields following the application of composts, while quite often no response is

obtained. Primary responsible for this irreproducibility have been indicated the

very high variability of the composition and properties of compost and of its

rate and method of application. Other important factors influencing negatively

reproducibility are the extreme variability of soil composition and properties,

crop requirements, and geoclimatic conditions. A general explanation proposed for

variability and irreproducibility of crop response to o.m. addition to soil is

that the potential of the organic fertilizer in improving plant growth conditions

is not effective when growing parameters are optimal, but it contributes to

maintain the maximal yield when conditions are out of the limits of the optimal

range (6).
526

ORGANIC WASTE COMPOSTATION AND COMPOSTS

From the previous discussion, it results clearly that organic residues and

wastes of any source should be adequately treated previous their addition to soil

in order to minimize adverse or dubious effects on soil properties, to avoid

potential induced phytotoxicity problems and destroy both plant and animal patho-

gens, and to maximize soil fertility functions. This means that, in order to

limit their environmental impact and to optimize their action as soil fertilizer,

organic additives should be characterized by composition, properties and behavior

in soil as close as possible to native soil o.m., and particularly humus, which

is the main responsible for soil organic fertility.

This goal may be achieved by subjecting raw organic materials to suitable

composting processes, which are able to produce a mature, stabilized final

product with a high "humic" character, the so-called "mature compost".

Substrate materials

Virtually, any organic waste material of biological origin and many synthetic

organic products are biodegradable and may be used as substrate material for

composting. Limitations on the use of a particular waste are the presence of

materials incompatible with composting, such as inert materials, plastics, glass,

metal objects, and hazardous compounds, such as heavy metals or not biodegradable

toxic organic substances, e.g. detergents, surfactants, phenolies, hydrocarbons,

pharmaceutics, etc., which pose a health risk either directly or through their

metabolic, degraded products. Starting materials should therefore be selected so

that they will not contaminate the compost produced, pollute the soil, be toxic

to plants, and represent an health hazard for animals and man. Conditions less

limiting than for agricultural use in field soil may be permitted, however, for

ornamental plants or reclamation of mine spoils and revegetation of other problem

areas, highway banks and dredged sediments as well as in forest fertilization(3).

The main types and sources of raw materials used for composting comprise: (a)

agricultural wastes, including crop residues and animal manures; (b) urban wastes

which include the organic fraction of urban solid refuses, sewage sludges from

anaerobic or aerobic digestion sewage treatment plants, and city refuses of green

areas; (c) wood processing wastes, including bark, woodchips, wood shavings and

sawdust; (d) food processing residues from canning industry, breweries, malt
 527

houses, dairying industries, fish and shell-fish wastes, slaughter-houses efflu-

ents and residues, sugar industry wastes and effluents, etc.; (e) other light

industry wastes, e.g. fermentation wastes, paper and cellulosic residues, vegetal

tannery sludges, etc.; and (f) local organic waste products, such as vine canes,
olive marc, rice hulls, cocofibre dust, tea wastes, etc.

Composting process

Composting is generally defined as "the biological oxidative decomposition of

organic constituents in wastes of almost any nature under controlled conditions"

(7). The qualification "biological" characterizes composting from purely physical

and/or chemical treatments, while its being largely aerobic distinguishes this

process from fermentation or anaerobic digestion. Furtherly, control of process

conditions differentiates composting from natural decomposition such as it occurs

in open dumps, manure heaps or field soil.

Composting is, therefore, a form of organic waste stabilization that requires

special conditions, particularly of temperature, moisture, aeration, pH and C/N

ratio, related to optimum biological activity in the various stages of the

process. During composting the heterogeneous organic substrate evolves through

three principal phases: (a) an initial phase during which readily degradable com-

ponents are decomposed; (b) a termophilic phase, during which largely cellulosic

and similar materials are degraded by a high biooxidative activity of microorgan-

isms with production of CO 2, H20 and inorganic species, release of phytotoxins,

destruction of animal and plant pathogens, and maintainance of the most stable

original organic compounds; and (c) a maturation and stabilization phase, which

is characterized by temperature decline, decomposition rate decrease, and recol-

onization of the mass by mesophilic microorganisms which lead to a stabilized

o.m. with humic-like nature. A subsequent, eventual stage is that of "curing" the

compost, which consists in a prolonged period of stabilization and mineralization

beyond the stage of maturity with production of a highly "humified" final product,

The term composting is generally not applied to anaerobic processes, including

fermentation and anaerobic digestion of organic wastes of any type, which greatly

differ from aerobic processes in terms of metabolic pathway and microbial popul-

ations involved. Products of anaerobic processes are characterized by resuming of

their metabolic activity with further oxidative stabilization and changes in com-

position and properties when exposed to aerobic conditions, i.e. in the field(8).
528

Composts

Compost may be appropriately defined as "the stabilized and sanitized product

of composting which is still in the process of stabilization and is beneficial to

plant growth". According to this definition, the o.m. in the product of compost-

ing must have been degraded to fine particles, have lost its original identity

and extensively stabilized to a humus-like product which can be applied on the

soil without damage to standing crops (8).

Products used in agriculture are taken at various stages of the composting

process and exhibit different properties and behaviour in soil. Organic material

before the termophilic stage is generally unsuitable for agricultural use for

reasons partly discussed previously in this paper.

"Fresh compost" may be defined as an intermediate product of the termophilic

stage, which has achieved sanitization where necessary, and has undergone partial

decomposition, but is not yet stabilized. This product may be used in agriculture

with further decomposition and stabilization occurring in soil with beneficial

effects on soil structure improvement, increased microbial activity, and gradual

release of nutrients through mineralization.

"Mature compost" is the end-product of the stabilization stage and can be

considered an organic fertilizer for general purpose being fully suitable for

application on the soil even in the presence of standing crops. Although, direct

contact with roots should be avoided for products derived from substrates such as

urban refuses, particularly in pot cultures, because it may cause a temporary

arrest of growth (8).

Finally, "cured compost" is defined as the highly stabilized product resulting

from a prolonged stabilization and mineralization stage, beyond that of commonly

accepted maturity. This material is often considered as a humus-like substitute

and thus has a high value for the preparation of artificial substrates used in

direct contact with root systems in nursery-protected crops, potting, and flower

cultivation.

Vermicomposting and vermicomposts

Vermicomposting is generally defined as "the biological degradation and stab-

ilization of organic matter that occurs as earthworms feed on organic waste mat-

erials". The most commonly used earthworm is Eisenia foetida, which lives natur-

ally in animal manure and has been applied successfully in vermicomposting of

 529

many organic wastes of vegetal and microbial origin, including urban refuses and

sewage sludges, food and paper manufacturing wastes, manures, etc.

The product of vermicomposting, i.e. vermicompost" or "wormcast" is finely

granulated and friable with only a faint pleasant earthy odour and shows increa-

sed humification rate and degree and a higher humic acid to fulvic acid ratio,

with the occasional presence of small quantities of growth regulators, i.e.

gibberellins, cytokinins and auxins (9,10).

COMPOST EVALUATION AS AN ORGANIC FERTILIZER

The principal requirement of a composted material to be safely and efficiently

used as an organic fertilizer is stability or maturity, which implies conversion

of o.m. to a more refractory, i.e. stable form, minimum content of phytotoxic

compounds and allelopathic chemicals and absence of plant and animal pathogens.

The question is how much should compost be stabilized before its utilization.

Obviously, this depends on many factors which should be both singularly and

globally evaluated in their effects on soil fertility and plant response.

A number of criteria and parameters have been proposed for testing stability

or maturity of the decomposing mass during the composting process and in the

final product, including C/N ratio, CEC, latent metabolism, latent toxicity,

presence of indicator organisms, and others. Since the stabilization or maturat-

ion phase implies the formation to some extent of humic-like substances and the

humified fraction of soil o.m. is the most important responsible for organic fer-

tility functions in soil, the evaluation of the "humification" degree of o.m. at

various stages of composting and in the final product is generally suggested as a

criterium of maturity and stabilization and a highly qualifying requisite for the

compost.

Since most of the proposed parameters and indexes are empirical and rather un-

satisfactory to furnish definite evidence of the formation of true HS in compost,

more reliable appears the evaluation of the quality of the "humified" o.m. in

compost on the basis of its analytical and physico-chemical characteristics, also

in comparison with those of native soil HS. Furtherly, application of advanced

spectroscopic methods, widely used to characterize native soil HS, are able to

better define the nature of "humic material" in compost.

530

Quality criteria and parameters

(i) The C/N ratio. The evaluation of the C/N ratio is the traditional

approach used for estimating compost maturity. A decline from the initial value,

which should be not ,30 in the substrate, to a final value ~20, generally indi-

cates an advanced degree of o.m. stabilization in the product and is considered

desirable for a mature compost (1,8). Care, however, must be used in the evaluat-

ion of C/N level changes for substrates rich in N, e.g. animal wastes and sludges

with initial C/N ratio often <lO, which tends to rise during the stabilization

process (8,11).

The C/N ratio itself is not, however, considered a reliable indicator of

compost maturity since raw materials used may have a wide range of lignin to cel-

lulose ratio and, therefore, varying biodegradability. Based on the consideration

that most biochemically active components of compost interact with plant roots

and microorganisms in the liquid phase, the evaluation of organic C/N ratio in

the water extract of compost has been considered more reliable than the global

C/N ratio (ll). Since an almost constant value of 5-6 was determined for the

organic C/N ratio in the water extract of various types of well-matured composts,

irrespective of the raw material, this value was proposed as a general index of

maturity (ll).

(ii) Cation exchange capacity (CEC). Since CEC of o.m. is mostly associated

to the presence of HS, which in turn depends on the degree of decomposition of

the organic substrate, this parameter has been suggested as a valuable index for

the estimation of compost maturity (12). CEC was found to increase with maturity

in composts from various raw materials, i.e. city refuse, pine bark, and pine

bark mixed with sewage sludges or residues of paper industries (13,14). A CEC

value , 6 0 meq/lO0 g was measured for city refuse composts considered sufficient-

ly matured for utilization (13). Highly significant negative correlations were

established between CEC and C/N ratio of urban refuse composts (13) and, more

recently, between CEC/total C ratio and C/N ratio in various animal manures at

different maturation stages (15). In the latter experiment, a value of CEC/total

C ,1.8, corresponding to a C/N ratio (15, was considered suitable for maturation

in manure (15).

(iii) Latent metabolism. Incomplete stabilization of compost may lead to a

later resumption of metabolic processes when favourable conditions are restored,

e.g. after application to the soil, with various adverse effects for plant growth,
 881

Laboratory methods for the evaluation of latent metabolism include oxygen-uptake,

i.e. respiration activity, and heat production, i.e. self-heating capacity, both

of which are indicative of the amount of degradable o.m. still present, i.e.

inversely related to stabilization (8).

(iv) BioloEical tests for phytotoxicity. Metabolic toxins and orEanic acids,

particularly low molecular weight fatty acids, released durinE o.m. decomposition

may survive the stabilization stage, e.g. in urban refuse composts (16,17). The

ageing or maturity level of some bark end sawdust composts appear to hiEhly

affect the residual presence and activity of allelopathic chemicals, which may

inhibit plant growth, and fungicides , both naturally-occurrinE in the raw mater-

ials (18). Thus, plant and microbial bioassays highly compatible with products

obtained from various raw materials, including urban solid refuses, manures,

plant residues and sewage sludEes , have been developed for testing latent toxic-

ity and physiological compatibility with plants.

- +

(v) Other indicators. Alkaline phosphatase activity and NO3/NH 4 ratio were

found to be directly correlated with maturity of cattle manure compost. A low,

but increasing phosphatase value suggested that composting was near to completion

while a low and stable, or declining value indicated a poor composting process

and a poorly composted material (19).

A total N content higher than 0.6% (dry weiEht) with organic-N >90~ and a
- + +

NO3/NH 4 ratio in favour of the oxidized form with NH 4 < 0.04%, are considered
+
desirable for mature compost, while an hiEh presence of NH 4 seems indicative of

unstabilized material when the substrate have a low C/N ratio (8).

Humification degree indexes

Some indexes which are used for the evaluation of the "humification" level in

the material during composting and in compost include:

(a) humification ratio: Chum/Cot E x i00 ,

(b) humification index: CHA/Cor E x i00 ,

(c) percent humic acid (HA): C H A / C hmu x i00 ,

(d) humic acid (HA) to fulvic acid (FA) ratio: CHA/CFA ,

(e) RF index: RF = K6oo/CHA x lO00 ,

(f) optical absorbance ratio: io E K = io E K40 O- io E K600

The value C refers to total orEanic carbon in the material, measured by acid
ore
titration with potassium dichromate or permanganate solutions. The value Chum
532

refers to total humic carbon measured in the alkaline (NaOH and/or Na4P207 )

extract of the material. The values CHA and CFA refer to C in the HA and FA frac-

tionated by the traditional method of acid (generally H2SO 4) precipitation at

pH = 1-2 of the alkaline extract and separation of solid HA from the FA solution

by eentrifugation. The K values, i.e. optical absorbances measured at 600 and

400 nm, and RF values are estimated according to Kumada et al. (20).

Although these indexes may be of utility to follow the composting process for

a given substrate, their wide fluctuation in dependence of the substrate often

leads to overestimation and misleading interpretation of the true humification

level achieved in the composting mass and in the final compost. A large body of

evidence exist of alkaline coextraction and, eventually, partial acid coprecipit-

ation of not or incompletely humified components of o.m., the alkaline extract

thus resulting in a mixture of both humic and non-humic substances.

Since most of the coextracted non-humic materials are believed to remain

together with the FA in the acid soluble fraction of the alkaline extract, the

use of suitable resins such as polyvinylpyrrolidone (Polyclar T) or Amberlite

XAD-8, able to retain completely the brown-coloured, phenolic FA fraction, has

been recently applied to separate the non-humic compounds from true FA (21). On

this basis, a new humification index (HI) for o.m. has been developed and propos-

ed in the form : HI = CNH/CHA+F A. CNH and CHA+F A represent the organic C content

measured by dichromate acid titration, respectively, in the column eluate contai-

ning the organic fraction not adsorbed onto the resin or non-humic substances

(NH), and in the combined acid precipitated, alkaline-redissolved HA fraction and

resin-retained, alkaline-eluted FA fraction (21). The index has been tested for

the o.m. extracted from a variety of soils and composts at different stages of

maturation. In the case of soil o.m., it was always below the value of l, approa-

ching a value near zero for o.m. from well-humified soil horizons. For raw sub-

strates and partially mature materials from urban refuses and sewage sludges, HI

resulted in most cases > 2 or between 2 and l, while for a well matured manure, it

was always <l. A value of HI < 1 was thus considered adequate for mature compost

(21). Although the HI appears under many aspects more reliable than other matur-

ity indexes, it needs more extended experimentation to confirm its applicability,

while an intrinsic factor of uncertainty is given by its not accounting for non-

humic substances which may be acid-coprecipitated in the HA fraction.

Some pyrolysis ratios have also been used as humification indexes for compost.
 533

For example, ratios which include carbohydrate derivatives in the numerator and

aromatic and heterocyclic compounds in the denominator have been found to decre-

ase during composting of barley straw or pear-tree wood, approaching the ratios

measured for humic materials from natural soil samples (22).

Humic-like substances characterization

The most appropriate and reliable approach to the evaluation of the "humic"

character and behaviour of the compost and of its value as an organic fertilizer

is based on the identification of the chemical and structural composition and

functional properties, i.e. on the identity of the "humic-like" substances in the

compost, also in comparison with those of HS from native soil and compost-added

soil. For this purpose, numerous chemical, physico-chemical and spectroscopic

methods and techniques have been applied which are briefly surveyed in the

following sections, together with most representative information which may be

obtained on the HS in composted organic materials.

(i) Elemental and functional group composition, E4/E 6 ratio. Humic acids

extracted from composts and vermioomposts of various origin and aerobically or

anaerobically digested sewage sludges (23-30) show C, H, N, and S contents higher

and O, total acidity, COOH and phenolic OH group contents and atomic C/H and C/N

ratios lower than those commonly referred for soil HA (1,25,29). Humic acids iso-

lated from soils freshly or continuously amended with composted or sludge mater-

ials at various rates are characterized by elemental composition and acidic func-

tional group content intermediate between those of native soil HA and compost or

sludge material HA (25,29) (Table I), whereas they tend to approximate native

soil HA composition with increasing time after compost or sludge application (29,

31). The FA fraction isolated from a municipal refuse compost and various compo-

sted sewage sludges show C, 0 and COOH contents lower and H, N and S contents

higher than those typical of average native soil FA (27,32,33) (Table I). Unlike

HA fraction, the FA fraction of the sludge amended soil more resembled the sludge

derived FA than the typical soil FA (32,33) (Table i).

Contrasting results are reported for the E4/E 6 ratio of HA from various compo-

sted materials. E4/E 6 ratios higher than those commonly observed for natural soil

HA and FA were measured for HA from composted hay or straw (34) and vermicomp-

osted animal manures, municipal refuse and sewage sludge (30,35), and HA and FA

from anaerobically composted municipal refuses (25,36). Although values lower

534

TABLE i. Some compositional and functional properties of HA and FA extracted from

compost and sludge materials, amended and non amended soil.

Sample and C H N S 0 Tot.Acid. COOH Phen.OH E4/E 6

Origin % meq/g
a
HA,comp.urban refuse 56.2 7.1 6.2 --- 30.4 5.0 1.5 3.5 4.5

HA,untreated soil a 45.7 3.6 4.3 --- 46.4 6.5 3.2 3.3 4.1
a
HA,amended soil 49.7 4.1 4.7 --- 41.5 6.3 3.1 3.2 5.0
b
HA,anaer.dig.sludge 52.0 7.2 8.8 --- 32.0 2.4 0.9 1.4 3.8

HA,untreated soil b 49.2 4.9 3.9 --- 42.0 7.2 2.6 4.6 5.0
b
HA,amended soil 50.3 5.3 5.0 --- 39.4 4.0 2.2 1.8 5.1
c
FA,comp.sludge 40.8 6.6 2.8 8.2 41.6 --- 0.7 . . . . .
d
FA,soil average 45.7 5.4 2.1 1.9 44.8 --- 8.2 . . . . . .
c
FA,amended soil 36.0 7.9 4.7 6.0 45.5 --- 7.9 . . . . .

a(25), b(29), c(32), d(33).

than those of soil HA and FA were determined for HA from anaerobically-digested

sludges (29) and HA and FA from aerobic sludge and urban refuse composts (27,37).

(ii) Molecular weight distribution. Both HA and FA isolated from a number of

sewage sludge and composts obtained from various mixtures of wheat straw, urea,

poultry l i t t e r and other plant and animal waste materials showed Sephadex eluti-

on curves dominated by a peak of a high molecular weight (MW) organic fraction,

differently from elution curves commonly obtained from soil HA and FA (23,24,28).

These results were ascribed to the elevated presence in the compost of large-

sized, low-condensed lignin constituents with adsorbed peripheral lipidic and/or

peptidic chains, and not to polycondensed lignin degradation products typical of

native soil HS (23,24,28).

The elution curves on Sephadex gel G-lO0 of unfractionated o.m. extracted with

NaOH-Na4P207 from an aerobically composted urban waste, a clay loam soil and the

same soil amended with 5% compost showed significative differences in the relat-

ive peak intensity (36) (Fig. i). The soil humus curve was characterized by three

distinct bands attributed to mean apparent ~W of i00,000, 26,000 and 1,300, while

in the compost o.m. curve the peak corresponding to a ~W = 26,000 was not appar-

ent and the intensity ratio of the lO0,O00 to 1,300 peak was much higher than in

the soil humus curve. The relative intensity of the three peaks in the curve of

o.m. extracted from the compost-added soil was intermediate between that of soil
 535

100,000 humus and compost o.m. (Fig. i).

These results indicate the tendency

E of the high MW organic components in

0 compost to decrease in size after ad-

dition to soil and to approximate the

elution pattern of native soil o.m..

i J / ~ _ It was s u ~ e s t e d that the I00,000 to

1,300 peak intensity ratio might be

used as a humification index for

SO 100 150 200 250 compost o.m. after its addition to

E ~ vokm~(mO soil.

FiE. i. Sephadex G-IO0 elution pattern of A similar trend to decrease in

o.m. extracts from compost (a), soil (b),
size was also observed for the large
and soil + 5% compost (36).
molecular-size fraction of water sol-

uble organic compounds from sludge-amended soils on short-term experiments (38).

Over large periods of time (i0 to 30 weeks), however, the molecular size distrib-

ution changed little for the water soluble material which tends to become more

homogeneous both in molecular size and chemical composition (38).

(iii) Electrophoresis and Isoelectrofocusing (IEF). Humic acids obtained from

a mature city refuse compost and an organic sandy podzolic soil revealed large

differences in electrophoretic mobility data (26). The electrophoregram of soil

HA was characterized by an important portion of immobile HA, which indicated a

low mobility index in comparison with the higher index observed in the case of

compost HA (26).

Isoelectrofocusing (IEF) has been applied for the evaluation of HS quality in

various types of composted and vermicomposted wastes in comparison with native

soil HS (39-41). Combined HA+FA fractions from mature farmyard or poultry manures

and vermicomposts were characterized by IEF patterns showing a great heterogene-

ity of bands in the pH gradient region from 4.5 to 6.5, similarly to soil HS (39~

Combined HA+FA fractions isolated from raw sludges focalized only at pH lower

than 5.0, while a more heterogeneous IEF pattern was obtained for HA+FA from

mature, biooxidized or anaerobically-digested sludges, which was characterized by

a strengtheninE of bands in the region between pH 5 and 6.5, thus approaching, at

least partially, IEF patterns typical of soil o.m. (40).

(iv) Pyrolysis-~as chromatography-mass spectrometry (GC-MS). The chromato-

536

grams of pyrolisates of compost HA (30,42) were different from those of soil HA

(43-45), being characterized by the predominance of methoxy- and dimethoxy-phenol

pyrolysis products typical of lignin and/or lignin residues, with minor amounts

of proteins, carbohydrates, tocopherols and some microbially-synthesized phenols,

which indicated an incomplete degradation or selective preservation of grass

lignin during vermicomposting.

GC-MS analysis of either pyrolisates of HS from sludge from olive mill waste

water (46) or persulphate degradative oxidation products of HA from composted

municipal refuse and from a soil added with the latter compost (25) indicated a

much higher presence of saturated and unsaturated fatty acids, alkylpyridines and

lignin components than in native soil HA pyrolisates or oxidation products.

(v) Infrared (IR) and Fourier Transform-Infrared (FT-IR) spectroscopy. IR

spectra of HA from composted urban refuses and domestic sewage sludges differ

from those typical of soil HA for more intense aliphatic, amide and polysacchar-

ide bands and for a less intense band of carboxylate group (23,25,26,29,36).

Humic acids extracted from compost- or sludge-amended soil were characterized,

differently from the non-amended soil HA, by IR absorptions typical of compost

or sludge HA, but of lower intensity, thus indicating a partial incorporation of

components originated from the compost or sludge into native soil HA (2B,29,31).

The HA fraction isolated from wheat straw composted in the presence of various

N-sources showed IR absorptions typical of wheat lignin and nitrogenated mater-

ials, while the FA fraction was characterized by IR spectra similar to those of

soil FA, with lignin bands of relatively low intensity, no evident amide absorp-

tions and relatively intense COOH bands (24,28).

The FT-IR spectra of HA and FA extracted from composted poplar bark were sim-

ilar, respectively, to type I and type III IR spectra of soil HA and FA (47),

although some absorptions suggested the presence of lignin components (48). The

IR spectra of various vermicompost HA also resembled those of grass lignin and

type III IR spectra of soil HA (47), with a prevalence of aromatic to aliphatic

and carboxylate absorptions and intense amide and polysaccharide bands (30,35).

The IR spectra of anaerobic sewage sludge FA were generally similar to type

III IR spectra of soil FA (47), but showed less pronounced carboxyl absorption

and more intense aliphatic, polysaccharide and amide bands, with respect to the

soil FA. Typical bands due to sulphonyl groups in these spectra, were retained in

the FA extracted from a soil amended with this sludge (32,49).

 537

(vi) IH and 13C nuclear magnetic resonance and 13C-CP-MAS NMR spectroscopy.

Solution IH and 13C-NMR spectra of FA extracted from anaerobically-digested

sludges gave evidence for significant amounts of both aliphatic and aromatic con-

stituents with prominent resonances due to polysaccharides and protein decompos-

ition products, while those due to carbonyl and carboxyl groups were weak, relat-

ive to soil FA. This suggested a less oxidized and microbiologically unstable

state for sludge FA with respect to native soil FA (50).

13
Solution C-NMR spectra of HA extracted from a composted municipal refuse and

the compost-amended soil were qualitatively and quantitatively similar, with some

minor difference in relative band intensity in the aliphatic region (I00-0 ppm)

(25,51).
13
Recently, solid state C cross polarization "magic angle" spinning (CP-MAS)

NMR spectra of intact samples of municipal and tannery sludges and composts

showed the presence of four types of carbon: carbonyl C (180-160 ppm), aromatic C

(140-110 ppm), aliphatic C attached to -OH or -N (80-40 ppm), and nonsubstituted

aliphatic C (40-10 ppm) (52). Although aliphatic peaks were prominent in all

spectra, differences in the relative amounts of each C-type were evident between

various sludges. Aerobically-composted sludges showed a significantly reduced in-

tensity of the aliphatic-C, C-OH or C-N, and carbonyl-C region with respect to

the aromatic-C region. The spectrum of an anerobic tannery waste sludge was very

different from the other sludge or compost spectra, the major C-components being

represented by fatty acids with smaller amount of aromatic acids. Computer-simul-

ated spectra were also employed successfully to profile organic C functionalities

in intact sludge and composted materials. Finally, spectra were presented illu-

strating how an interrupted decoupling experiment could be effective in differen-

tiating between lignin and humic components in sludge or compost (52).

(vii) Electron spin resonance (ESR) spectroscopy. ESR spectra of HA and FA

from various vermicomposts, sludges, and sludge-amended soils indicated the pres-

ence of organic free radical species of the same chemical nature as those of

native soil HA and FA, i.e. semiquinonic moieties conjugated with a condensed

aromatic network (30,31). On the other hand, free radical concentration in vermi-

compost HA was one order of magnitude lower and in sludge-amended soil HA about

one half the amount commonly observed in soil HA (30,31,53).

Large scan range ESR spectra of sewage sludge FA, various vermicompost HA and

sludge-amended soil HA (Fig. 2) generally indicated evident differences, with

538

respect to those of native soil FA and HA

FO3 ~
(Fig. 2b), in the presence and relative int-

a ensity of paramagnetic metal ions (Fe 3+,

2+
Cu , VO 2+) resonances and in the nature of
[ 50mT ] 300 ml their binding sites (31,54-58). Significant

differences in the relative stability of

F
/REERADICAL metal complexes and residual metal oomplex-
ation capacity were also apparent in the ESR
VO2~ spectra of variously sludge-amended soil HA

Fe~* Cu z+ and the non-amended soil HA (31,55).

(viii) Fluorescence spectroscopy i Fluo-

~
150 roT] 500m711 /

F~ROE2E+RAD
C
IAL
scence analysis has been recently applied as

a useful method in obtaining structural and

chemical information on the groups respons-

ible for the fluorescent properties of HA

and FA of various nature and origin.

5 ~A0!2+~ Fluorescence spectra of HA from vermi-

~ y composted animal manures, sewage sludge and

; urban refuse and FA from anaerobically-dig-

5001ml ~ - ~ ested sludge resembled more those of soil FA

VO 2+
I
50m1
I I than those of soil HA, in that they were

consistent with the presence of fluorophores

E associated with aromatic structures of rel-

RADC
I AL
/ atively low degree of polycondensation and

humic evolution (59) (Fig. 3).

Fig. 2. Solid state ESR spectra at 77 K (scan range, 8000 G) of vermicomposted

manure HA (a) (54), non-amended soil HA (b) and sludge-amended soil HA (c) (31),

CONCLUSIONS AND RECOMMENDATIONS

Because of the quite vague characterization of composted materials and lack of

uniformity of parameters to be tested, graded and evaluated to define the compost

quality, safety and efficiency as an organic fertilizer, answers are needed for

the definition of a valid, comprehensive and uniform set of generally-accepted

parameters for the evaluation and specification of the organic fertilizing

 539

"~1 •

, 440
a i/ '/~"" /~"" . 4aS

i V / 43s \\
-
cI)
\
>

= _4oo , 460 , , 520 , 350 , 450

wavelength (nm) wavelength (nm)
Fig. 3. Emission ( ~ = 360 nm) (left) and excitation ( A = 520 nm) (right)
ex
fluorescence spectra o~ soil HA (a, a' ), manure vermicompose~ HA (b, b' ), soil
FA (c, c') and composted sewage sludge FA (d, d' ) (59).

quality and capacity of the composted material. Efforts should be oriented pref-

erentially to gain detailed compositional, structural and functional information

on the "humic" fraction of the o.m. both during its evolution in the composting

process and in the final product, by a more extended application of introspective

advanced physico-chemical and spectroscopic techniques.

The individuation of not yet available models is needed to describe and estim-

ate the fate of added o.m. in the soil-compost system, possibly based on similar

o.m.-transformation models available for the decomposition of fresh plant

residues.

Essential also appears to rationalize the use of compost by providing adequate

specifications and instructions to the utilizers in order to obtain the best

response in improving soil fertility, crop production and environment protection.

In conclusion, standing the enormous potential of organic waste supply from

urban, agricultural, forest and food sources, any effort to increase and amelior-

ate the fertilizer application of compostsd materials in agriculture should be

highly encouraged.

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540

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