NOTAS DE AULA - SOL 250 Constituição, Propriedades e Classificação de Solos
QUÍMICA DO SOLO
Profº Ivo Ribeiro da Silva Viçosa - MG 2008-I
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ÍNDICE 1. INTRODUÇÃO ........................................................... ....................................................................................................................... ...................................................................................1 .......................1 2. COMPOSIÇÃO QUÍMICA DO SOLO..........................................................................................................3 3. FRAÇÕES GRANULOMÉTRICAS DO SOLO............................................................................................5 3.1. Composição mineralógica das frações granulométricas do solo.............................................................6 solo.............................................................6 4. SISTEMA COLOIDAL DO SOLO..............................................................................................................10 4.1. Propriedades de um Sistema Coloidal....................................................................................................10 5. FRAÇÃO FRAÇÃO ARGILA DO SOLO ......................................................... .................................................................................................................. ...........................................................12 ..12 5.1. ARGILAS SILICATADAS ............................................................................................................................12 i. Argilas do tipo 2:1. .............................................................................................................................13 .............................................................................................................................13 ii. Argilas do tipo 1:1 .............................................................................................................................16 5.2. ARGILAS NÃO SILICATADAS .....................................................................................................................17 6. MATÉRIA ORGÂNICA DO SOLO .......................................................... ............................................................................................................ .................................................. 18 6.1. Compartimentos da matéria orgânica do solo (MOS) ...........................................................................21 ...........................................................................21 i. Matéria orgânica viva ......................................................... ..................................................................................................................... ............................................................21 21 ii. Matéria orgânica morta .................................................................................................................23 6.2. Rotas de formação formação e características características das substâncias húmicas ............................................................ ................................................................27 27 húmicas...........................................................28 6.3. Características químicas e estruturais das substâncias húmicas...........................................................28 6.4. Mecanismos de estabilização da MOS .................................................................... ................................................................................................... ...............................34 34 i. Estabilização química ou coloidal...................................................................................................34 coloidal...................................................................................................34 ii. Estabilização física......................................................................................................................... física.........................................................................................................................36 36 iii. iii. Estabilização bioquímica ..............................................................................................................38 6.5.Propriedades do solo influenciadas pela matéria orgânica do solo (MOS) ........................................... ...........................................39 39 a). Propriedades químicas...................................................................................................................39 i. Capacidade tampão .....................................................................................................................39 .....................................................................................................................39 ii. Capacidade de troca catiônica ............................................................. ................................................................................................... ......................................41 41 iii. Complexação de metais ......................................................... ............................................................................................................. ....................................................41 41 b). Características físicas do solo..................................................................................................... solo.................................. ...................................................................... ...44 44 i. Agregação....................................................................................................................................44 Agregação....................................................................................................................................44 ii. Retenção de água........................................................................................................................64 água........................................................................................................................64 7. ORIGEM E FORMAÇÃO FORMAÇÃO DAS CARGAS ELÉTRICAS ELÉTRICAS DO SOLO SOLO ...................................................... .........................................................76 ...76 7.1. ORIGEM DAS CARGAS NEGATIVAS ..........................................................................................................77 7.2. CARGAS POSITIVAS .................................................................................................................................78 7.3. DENSIDADE DE CARGA ............................................................................................................................79 8. INTERAÇÕES COLÓIDE/SOLUÇÃO: FENÔMENOS FENÔMENOS DE ADSORÇÃO E TROCA DE ÂNIONS E CÁTIONS......................................................................................................................................................79 8.1. CAPACIDADE DE TROCA CATIÔNICA (CTC)............................................................................................62 8.1.1. Características da CTC do solo solo ........................................................... ........................................................................................................ ............................................. 63 i. Valor T ...................................................... ..................................................................................................................... .......................................................................................... ...........................64 64 ii. Soma de Bases (SB)............................................................................................................................66 (SB)............................................................................................................................66 iii. Saturação por Bases Bases (V) (V) ............................................................ ................................................................................................................... .......................................................66 66 iv. Saturação por Alumínio (m)..............................................................................................................66 (m)..............................................................................................................66 v. Acidez Trocável ...................................................... ....................................................................................................................... ............................................................................ ...........67 67 vi. Acidez Potencial ................................................................................................................................67 Potencial ................................................................................................................................67 8.1.2. Fatores que afetam a capacidade de troca catiônica.........................................................................68 8.2. CAPACIDADE DE TROCA ANIÔNICA (CTA) ........................................................... .......................................................................................... ............................... 68 8.3. DUPLA CAMADA DIFUSA (DCD) ................................................ ..................................................................................................... ..................................................... 70 8.4. PONTO DE CARGA ZERO (PCZ)..................................................................................................................71 8.3. DISPERSÃO E FLOCULAÇÃO DAS PARTÍCULAS DO SOLO............................................................................72
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9.1.1. Fontes de Acidez do Solo.............................................................................................................73 a) Minerais de Argila .......................................................................................................................................... 74 b) Matéria Orgânica............................................................................................................................................ 74 c) Ácidos Solúveis.................... Solúveis.......................................... ........................................... ........................................... ........................................... .......................................... ...................................... ................. 74
9.1.2. Fontes de Alcalinidade no Solo....................................................................................................75 9.2. Capacidade Tampão da Acidez do Solo..........................................................................................76 9.3. Causas da Acidificação Progressiva dos Solos................................................................................76 9.4. Problemas Causados pela Acidez do Solo.......................................................................................77 9.5. Calagem...........................................................................................................................................77 10. REAÇÕES DE OXIDAÇÃO E REDUÇÃO REDUÇÃO NO SOLO SOLO ............................................................... ............................................................................78 .............78 BIBLIOGRAFIA CONSULTADA .................................................... ................................................................................................................ ..............................................................79 ..79
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1. Introdução O solo é um corpo natural formado pela interação da atmosfera, hidrosfera e biosfera com os materiais da litosfera (Figura 1). Sua constituição química reflete, portanto, a contribuição de cada fator de formação (tempo, material de origem, clima, atividade biológica, relevo) variando quimicamente de acordo com a natureza desses fatores.
Solo = ∫ [T , MO, Cl , Org , R ]
Influência da litosfera Influência da atmosfera/hidrosfera Influência da biosfera
Figura 1. Influência dos fatores de formação do solo. As rochas situadas na superfície terrestres são vulneráveis a processos físicos, químicos e biológicos (intemperismo) que resultam na alteração e desintegração dos minerais originalmente presentes, resultando r esultando na formação de novos minerais e na liberação de íons (cátions e ânions). Esses processos que ocorrem na superfície terrestre são responsáveis pela formação do solo (Figura 2).
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Figura 2. Avanço do intemperismo e formação do solo. O solo é um sistema trifásico composto pelas fases, sólida (minerais e material orgânico), líquida e gasosa. Um solo mineral, próximo à superfície apresenta, aproximadamente, a seguinte composição volumétrica: 50% de espaço poroso - ocupados por partes iguais de ar e de água; 45 a 48% de sólidos minerais e 2 a 5% de material orgânico. Têm-se, normalmente, então, 50 % constituídos pela fase sólida, 25% pela fase líquida e 25% pela fase gasosa (Figura 3).
Figura 3. Proporções das fases sólida, líquida e gasosa do solo (Murphy, 1980). A fase sólida é constituída por materiais minerais derivados das rochas ou sedimentos
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A fase líquida, denominada solução do solo, é formada pela água proveniente da atmosfera ou corpos corpos d’água e lençol freático, acrescida de minerais e compostos compostos orgânicos dissolvidos. A fase gasosa ou atmosfera do solo é composta pelos gases presentes no espaço poroso. Apresenta composição diferente da atmosfera do ar em função dos gases produzidos pela atividade biológica (respiração microbiana e respiração de raízes) e reações químicas que ocorrem na solução do solo, podendo conter de 10 a 100 vezes mais CO 2 que na atmosfera livre. A estrutura, textura e a porosidade do solo, assim como a presença de água, afetam as taxas de difusão destes gases para a atmosfera.
2. Composição química do solo A composição química da fase sólida é em grande medida determinada pelos materiais de origem do solo. A fase sólida é proveniente dos materiais derivados das rochas e /ou sedimentos, associados aos compostos de origem orgânica (Figura 4). A constituição química das rochas ou sedimentos é variável em função de sua origem e natureza, afetando as características do solo formado. Esta influência tende a se reduzir na medida em que o intemperismo atua, podendo levar solos derivados de materiais de origem diferentes a apresentarem feições e composição química similares.
Fragmentos do material de origem Fração orgânica pronunciada.
Horizonte B com maior expressão de desenvolvimento pedogenético
Material de origem
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primários das rochas e sua transformação em minerais secundários. Em condições de temperatura elevada associadas à intensa precipitação o intemperismo é acelerado. Isso pode ser bem verificado em solos de regiões tropicais e se, associado associado à alta atividade biológica o processo processo tende a ser ainda mais acelerado. Nestas condições os minerais primários de fácil intemperismo são destruídos, restando apenas aqueles de elevada resistência ao intemperismo. A figura 5 mostra a atuação do intemperismo e um resumo do ciclo dos nutrientes no solo.
Figura 5. Atuação do intemperismo e ciclo dos nutrientes no solo (CEFET, PR). Nos solos, em geral, há uma predominância de Si e Al devido a abundância destes
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Quadro 1. Composição química dos solos. Adaptado de LINDSAY (1979). Elemento Químico
Peso atômico ...........g..........
Alumínio Carbono Cálcio Ferro Potássio Magnésio Manganês Nitrogênio Oxigênio Fósforo Enxofre Silício Titânio
Concentração na Faixa de Concentração litosfera comum nos solos ................................g ................................g kg -1.................................
26,98 12,01 40,08 55,85 39,10 24,31 54,94 14,01 16,00 30,97 32,06 28,09 47,90
81,0 0,95 36,0 51,0 26,0 21,0 0,90 465,0 1,20 0,60 276,0 6,0
10– 300 – 7– 500 7– 550 0,40 – 30 0,60 – 6 0,02 – 3 0,20 – 4 – 0,20 – 5 0,03 – 10 230 – 350 1– 10
Como comentado anteriormente, a influência do material de origem na composição do solo decresce à medida que estes sofrem efeito do intemperismo. Solos pouco intemperizados preservam ainda minerais primários que servem como fontes de nutrientes para as plantas. Os solos tropicais muito intemperizados praticamente não contêm minerais primários facilmente intemperizáveis (MPFI), sendo constituídos quase exclusivamente por minerais secundários (argilas silicatadas, óxidos) e quartzo (Quadro 2).
Quadro 2. Relação entre material de origem e minerais do solo. Presença nas frações do solo Baixo Intemperismo
Alto Intemperismo
Elementos Predominantes
Quartzo
Areia
Areia
Si, O
Feldspatos
Areia/silte
-
Si, O, Al, Ca/Na.
Minerais Primários
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após a dispersão dos agregados. Limites de tamanho definem as partículas como pertencentes a diferentes frações. Esses limites são estabelecidos pela classificação de Atterberg ou classificação internacional (Quadro 3 e Figura 6).
Quadro 3. Limites dos tamanhos das partículas dos solos, considerando a classificação Brasileira.
Terra Fina Argila
Silte
Areia Fina
Areia Grossa
Cascalho
............................................ ................................................................ .................... mm ............................................. .................................................................... ........................... .... ≤ 0,002 0,002 - 0,05 0,05 – 0,2 0,2 - 2,0 >2
Figura 6. Esquema representativo da diferença de tamanho entre as frações granulométricas do solo. 3.1. Composição mineralógica das frações granulométricas do solo A composição mineralógica das frações granulométricas está relacionada ao o grau de intemperismo do solo. O processo do intemperismo leva à fragmentação física e decomposição
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(a)
(b)
(c) Fonte: Decifrando a Terra
Figura 7. Exemplos da ação do intemperismo físico (a e b) e químico (c). A fração areia pode conter minerais primários, originados do material de origem do solo, no caso dos solos pouco intemperizados. Com o avanço do intemperismo, apenas o quartzo se mantém nesta fração (Figura 8). Os minerais de menor resistência ao intemperismo, como os feldspatos, piroxênios, olivinas e biotita, se decompõem em minerais secundários. Na fração grosseira podem ser também encontrados nódulos e concreções formados pedogeneticamente pela cimentação por óxidos de ferro presentes presentes nas frações frações mais finas. A fração silte é composta por fragmentos de minerais do material de origem e/ou
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a
Fração areia: Solos pouco intemperizados: quartzo e fragmentos de materiais de origem (minerais rimários
Fração silte: Solos pouco intemperizados: fragmentos de materiais de origem (minerais primários) Solo Soloss muit muitoo inte intem m eriz erizad ados os:: micr microa oa re ados ados
Fração argila: Solos pouco intemperizados: argilas 2:1, argilas1:1 e óxidos Solos muito intemperizados: argilas 1:1 e
b)
Figura 8. a) Fotomicrografia de secção fina de latossolo, observada em microscópio ótico, e; b) fotomicrografia de um grão de um mineral qualquer, coberto por cristais de quartzo e por argila, neste caso, caso, a esmectita. A fração argila é composta por minerais secundários originados do intemperismo dos minerais primários. O processo de formação dos minerais secundários se dá pelo rompimento da rede cristalina destes e pela remoção dos íons pela água que atravessa as fraturas nas rochas. Em
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Figura 9. Este esquema ilustra o avanço do intemperismo i ntemperismo e as transformações dos minerais. A transformação de minerais 2:1 em 1:1 também depende das condições locais de drenagem e da razão remoção/acumulação dos produtos de decomposição, podendo ocorrer reversão desse processo em locais de acúmulo, como depressões e áreas mal drenadas. No final do intemperismo i ntemperismo ocorrem condições favoráveis à transformação das argilas 1:1 em hidróxidos de alumínio (gibbsita). Solos em estágio de intemperismo avançado são predominantemente predominantemente oxídicos, como alguns Latossolos, nos quais se verifica uma concentração relativamente elevada dos óxidos de ferro e alumínio devido à remoção dos demais elementos pelo intemperismo. Certas condições de intemperismo podem levar os minerais primários
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A argila é a fração f ração mais importante do solo. Suas propriedades físicas e químicas, como a retenção de umidade, capacidade de troca iônica e as propriedades como a friabilidade, plasticidade e pegajosidade pegajosidade são derivadas de sua sua natureza coloidal. coloidal.
4. Sistema coloidal do solo O solo pode ser considerado um sistema disperso, pois é constituído de mais de uma fase, sendo que a fase sólida está em estado de acentuada subdivisão. Há, portanto, um sistema coloidal1/ no solo, constituído de partículas diminutas, de tamanho coloidal (inferior a 2 µm), minerais ou orgânicas, ou organo-minerais, como fase dispersa na solução (ou no ar) do solo, como meio de dispersão. Nesse sistema ocorrem reações químicas, físico-químicas e microbiológicas de imensa importância no estudo dos solos. Neste tamanho, os materiais adquirem propriedades particulares, relacionadas ao aumento relativo da superfície específica e ao pequeno tamanho das partículas.
4.1. Propriedades de um Sistema Coloidal a) Superfície Específica O termo superfície específica refere-se à área por unidade de massa do material considerado (solo como um todo, fração argila apenas, matéria orgânica etc.) e é, usualmente,
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Figura 11. Importância do tamanho da partícula na atividade da argila. Quanto ao tipo de mineral de argila presente, sabe-se, por exemplo, que a caulinita apresenta superfície específica de 10 a 30 m 2/g, os óxidos de Fe de 100 a 400 m 2/g, e a montmorilonita, no outro extremo, de 700 a 800 m 2/g, segundo citações de Grohmann (1975). É de se esperar, portanto, que solos tropicais, que têm nos óxidos e na caulinita os maiores constituintes da fração argila, tenham menor superfície específica, em geral, que solos de regiões temperadas, onde há predominância de montmorilonita e de outras argilas silicatadas mais reativas (Quadro 4).
Quadro 4. Área superficial específica (ASE) e Capacidade de Troca Catiônica (CTC) de constituintes da fração argila do solo.
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Propriedade muito importante de uma dispersão coloidal é a presença de cargas elétricas. As partículas coloidais do solo, as argilas de modo geral, são eletronegativas. Embora possam, também, possuir cargas positivas, estas são, normalmente, em menor número. Em alguns solos, com um grau de intemperismo avançado, pode-se encontrar um maior número de cargas positivas do que negativas, entretanto tal situação não é representativa do normalmente observado.
c) Cinética As partículas dispersas em meios líquidos apresentam movimentos (Shaw, 1975). O movimento browniano é caracterizado pelo movimento brusco, irregular e em zigue-zague de partículas individuais no meio de dispersão. Esse movimento deve-se à energia cinética das partículas. O movimento de difusão é conseqüência da migração de partículas de uma região de maior concentração para outra de menor concentração. Há, também, o movimento ocasionado pela força gravitacional, gravitacional, responsável responsável pela sedimentação sedimentação de partículas.
5. Composição química, estrutura e origem das cargas em colóides do solo. Os colóides podem ser divididos quanto à sua origem em inorgânicos e orgânicos. No solo, entretanto, ambos estão associados, podendo formar complexos organominerais estáveis (Figura 12). Estes complexos podem estar unidos por ligações químicas relativamente fortes,
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Silício Oxigênio
Alumínio Oxigênio
Figura 12. Tetraedro de silício e octaedro de alumínio. (Fonte: www.pubpages.unh.edu) www.pubpages.unh.edu) Os tetraedros podem ligar-se entre si, formando uma camada contínua, seguindo duas direções no espaço, constituindo a estrutura dos filossilicatos. A ligação dos octaedros entre si também dá origem a uma camada semelhante à anterior. O número de camadas de tetraedros para camadas de octaedros, por unidade componente de um cristal de argila silicatada, é uma característica básica de identificação dos principais grupos de argilas silicatadas (Pinto, 1967; ANDA, 1975; Moniz, 1975). Sendo as argilas
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Tetraedros Tetraedrosdedesilício silício
Octaedros de alumínio Tetraedros de silício Fonte: www.pubpages.unh.edu www.pubpages.unh.edu
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a)
b)
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anteriores, porém contendo polímeros de alumínio (ou magnésio no caso da clorita) entre suas camadas, que estabilizam sua estrutura e impedem sua expansão. São mais resistentes aos intemperismo e podem ser encontrados em pequenas quantidades em Latossolos. O preenchimento do espaço entrecamadas de argilominerais do tipo 2:1 produz modificações nas propriedades químicas e físicas desses minerais, tais como: reduz a carga permanente, diminuindo a CTC; aumenta a carga variável, possibilitando a fixação de ânions e metais pesados; reduz a área superficial interna e a capacidade de expansão e contração.
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a) Octaedro de alumínio
Mineral 1:1 (caulinita)
Tetraedro de silício Pontes de hidrogênio
Mineral 1:1 (caulinita)
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alumínio. Podem ter tamanhos e grau de cristalinidade variados, podendo ser encontrados como cristais isolados, como recobrimento de agregados e partículas, formando cimentantes, ou ainda associados à matéria orgânica.
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microorganismos (vírus, bactérias, bactérias, fungos, algas, protozoários, protozoários, nematóides). nematóides). Isto sem considerar o imenso volume ocupado pelas raízes das plantas. Todos estes elementos, minerais e biológicos, encontram-se em profundo entendimento, numa intensa relação de trocas. O desenvolvimento dos organismos vivos, por exemplo, depende da presença dos minerais, água e o ar do solo. Por outro lado, a atividade dos organismos vivos promove um aumento da fertilidade do solo por meio da ciclagem de nutrientes contidos em materiais vegetais. Os organismos do solo atuam como transformadores produzindo a matéria
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dependente das taxas de ciclagem do C. Em termos globais, o C está armazenado nos compartimentos: oceânico (38.000 Pg); geológico, principalmente petróleo, gás natural e carvão mineral (5.000 Pg); biosfera, solo (2.500 Pg) + biota terrestre (560 Pg); e atmosférico (760 Pg) (Lal, 2004).
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sua dinâmica, a MOS pode ser divida em diferentes compartimentos que se distinguem entre si quanto à função, natureza, reatividade, distribuição espacial, biodisponibilidade, entre outros aspectos (Stevenson, 1994). Uma divisão mais geral pode ser feita separando-a em dois componentes: matéria orgânica viva e morta.
6.1. Compartimentos da matéria orgânica do solo (MOS) Num sentido bem amplo a MOS pode ser ser entendida como a fração que compreende compreende todos
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rica em cátions (Quadro 6), promovendo também, melhoria na característica química do solo (Quadros et al., 2000).
Quadro 6. Características químicas dos excrementos de minhoca e do solo (Quadros et al., 2000). Amostras Excr Excrem emen ento to 0-5 0-5 (cm) (cm)
pH CaCl 3,4 3,4 4,1 4,1
Al Ca Mg Na K CTC -1 ……………mmolc kg ………………. 20,5 20,5 12,5 12,5 10 0,6 0,6 1,8 1,8 45,4 45,4 7,5 7,5 1 1 0,2 0,2 0,6 0,6 10,3 10,3
P mg kg-1 19 17
C g kg-1 33,1 33,1 11,7 11,7
m % 45 73
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O C-BM representa um dos compartimentos da MOS com menor tempo de ciclagem, o que o torna sensível à mudança de manejo do solo, sendo proposto como um indicador, à curto prazo, das mudanças da MOS (Tótola & Chaer, 2002). A BM responde rapidamente às práticas de manejo que levam ao decréscimo da MOS. Uma vez que a MOS constitui-se na fonte energética dos organismos, além da quantidade, comumente alterada pelas práticas de manejo, a qualidade do material orgânico adicionado terá uma forte influência no tamanho da população e na atividade dos organismos do
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Dentre os vários extratores empregados na extração e fracionamento das SH, o mais -1
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6.2. Rotas de formação e características das substâncias húmicas
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s o r
Resíduos de plantas e microbianos Rota Degradativa
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As cargas eletropositivas do solo têm sua origem nos óxidos e hidróxidos (óxidos hidratados) de Fe e de Al, Al , preferencialmente. Tal situação se dá de maneira mais significativa em condições mais ácidas de solo (Jarward e Reisenauer, 1966).
Esse esquema mostra que os óxidos hidratados de Fe e de Al podem dar origem a cargas eletropositivas, eletronegativas ou permanecer com carga neutra na superfície, dependendo do pH do solo.
7.3. Densidade de Carga A densidade de cargas negativas é a quantidade destas cargas por unidade de superfície de um material. Pode ser expressa em mol c/m2 ou em C/m 2. O molc negativa corresponde a 9,6485 x 104C (Coulomb). Por exemplo, a caulinita tem 1,93 x 10 -3C/m2.
8. Interações colóide/solução: fenômenos de adsorção e troca de ânions e cátions. As propriedades de adsorção iônica do solo são devidas, quase que totalmente, aos minerais de argila e à matéria orgânica coloidal do solo, materiais de elevada superfície específica. Essas partículas coloidais do solo apresentam cargas elétricas negativas e positivas, podendo adsorver adsorver ou "reter", por diferença diferença de carga, tanto cátions como ânions ânions (Figura 42). As cargas negativas são neutralizadas por íons eletropositivos, ou seja, pelos cátions, o que se denomina adsorção catiônica . Na neutralização de cargas positivas pelos ânions tem-se a
adsorção aniônica . Os íons envolvidos nesse processo de adsorção ligam-se por eletrovalência ou por covalência às partículas coloidais do solo. Os cátions mais envolvidos quantitativamente nesse processo são: Ca 2+, Mg2+, Al3+, H+, K +, Na+ e NH4+, sendo o Ca 2+, comumente, o mais abundante em alguns solos, enquanto que, em outros, o Al 3+ predomina. Alguns micronutrientes estão, também, sujeitos ao mesmo processo, embora em quantidades muito pequenas, se
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Figura 42. Esquema representativo da movimentação iônica no solo, evidenciando os três mecanismos pelos quais as plantas conseguem absorvê-los. (Fonte: www.interactive.usask.ca). www.interactive.usask.ca). Como as cargas da fase sólida se manifestam na superfície das partículas (micelas) do solo, há estreita relação entre o fenômeno de troca e a área superficial dessas micelas. Essa área expressa em m 2 g-1, é a superfície específica do solo (Quadro 7). Assim, o fenômeno de troca iônica do solo, que é basicamente a expressão de suas propriedades físico-químicas, é função de sua superfície específica e da densidade de cargas elétricas que se manifestam nesta superfície.
Quadro 7. Área superficial específica (ASE) e Capacidade de Troca Catiônica (CTC) de constituintes da fração argila do solo PARTÍCULA Caulinita Óxidos
ASE m2 g-1 7 – 30 –
CTC cmol c kg-1 0–1 2–4
Micas
40 – 150
10 – 40
Vermiculita
50 – 800
100 – 150
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Esquematicamente, Esquematicamente, o fenômeno de adsorção e troca iônica pode ser representado:
a) Troca Catiônica
b) Troca Aniônica
Embora ânions como NO 3-, SO4= e Cl- possam se comportar como cátions, sendo trocáveis e obedecendo às mesmas condições discutidas para a CTC, alguns ânions importantes como os fosfatos e molibdatos sofrem uma adsorção aniônica (figura 43). Nestes últimos ocorre a formação de complexos de esfera interna, onde o íon perde a camada de hidratação ao se ligar diretamente ao sítio de troca, o que resulta em uma ligação mais forte e estável (uma combinação de ligações covalentes e iônicas). As principais características desta ligação são: a. Especificidade. b. Influência das características da superfície e do ânion. c. Não obediência obediência aos princípios de estequiometria e reversibilidade. reversibilidade.
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Figura 43. Representação da adsorção aniônica no solo. 8.1. Capacidade de Troca Catiônica (CTC) A CTC do solo é responsável pela retenção e liberação dos cátions dos colóides para a solução do solo, permitindo sua maior permanência no sistema de forma a serem absorvidos pelos microorganismos e plantas, e reduzindo sua progressiva lixiviação. li xiviação. Estas ligações se dão pela formação f ormação de complexos de esfera externa (interação onde o cátion mantém sua camada de hidratação e se liga por forças eletrostáticas) entre os cátions, como Ca +2, Mg+2, K +, NH4+, e a superfície dos colóides. Suas principais características são: a. Estequiometria: as reações sempre ocorrem de forma estequiométrica, ou seja, para cada mol de carga (mol c) adsorvido há um mol c dessorvido. Assim, um íon Ca 2+ na solução do solo pode trocar com dois íons K + que se encontram adsorvidos à superfície do colóide. È importante lembrar que:
mol c =
mol valência
b. Velocidade: as reações são rápidas. c. Independência de temperatura: Mudanças de temperatura dentro de uma faixa estreita não afetam de forma expressiva seu comportamento. d. Reversibilidade: as reações são prontamente reversíveis, permitindo o deslocamento de íons para a solução e a adsorção de novos cátions.
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dado pH, parte das cargas dependentes estará bloqueada por H: (ligações covalentes). Desta forma, a CTC do solo nesse pH será dada pelas cargas permanentes mais àquelas dependentes de pH, porém livres do hidrogênio covalente, constituindo a CTC efetiva do solo, a esse valor de pH. E, quando se aumenta o pH do sistema, mais íons H + ligados a cargas dependentes do pH são neutralizados, resultando num conseqüente aumento da CTC efetiva do solo. Dentre os cátions que neutralizam as cargas negativas da CTC efetiva do solo, incluemse, principalmente, as bases (Ca 2+, Mg2+, K +, Na+ e NH4+), o Al3+ e, também, cátions H + ligados a cargas negativas da CTC de caráter mais eletrovalente (tipo ácido forte). Ao conjunto dos cátions que estão ocupando a CTC do solo, saturando-a, juntamente com as cargas negativas dos colóides denomina-se complexo sortivo do solo. solo. Quando se usa usa uma solução solução salina não tamponada, como como KCl 1 mol/L mol/L ou CaCl 2 0,5 mol/L, para a determinação da CTC do solo, o valor obtido corresponderá à CTC efetiva. Por outro lado, se a solução salina for tamponada a um definido pH, o valor obtido corresponderá à CTC total do solo naquele pH, englobando a CTC permanente e a CTC dependente do pH. Para determinar a CTC a pH 7,0, usa-se uma solução tamponada de acetato de cálcio 0,5 mol/L, ou de acetato de amônio 1 mol/L, pH 7,0. Na figura 44 é apresentado apresentado um esquema esquema que ilustra os conceitos discutidos: discutidos: pH do solo → |← ↓ Al3 +
|← CTC permanente
K+
Ca2 +
+
3+
H
NH4+
Al
Ca2 +
pH 7,0 CTC dependente de pH −H −H
−H
−H
H+
−H
→| −H
−H
−H
−H
−H
Mg2 + Mg2 + H+
−H
−H −H
−H
← CTC CTC efetiva →| ← CTC "bloqueada" → Figura 44. Representação esquemática da CTC de um solo de região tropical .
8.1.1. Características da CTC do Solo
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“T” para a CTC a pH 7,0 e por “t” para CTC efetiva, no pH do solo, a soma de bases (SB), o índice de saturação por bases (V), a acidez trocável (alumínio trocável), a acidez total (H + Al) e a saturação por alumínio (m). Esses valores, à exceção da saturação por alumínio, são conhecidos como valores de Hissink. Uma idéia da amplitude da variação das características relacionadas com a CTC do solo, bem como a divisão dessas características em classes, de acordo com a magnitude da mesma, para solos de regiões regiões tropicais, como como os do Estado de Minas Gerais, é dada no Quadro Quadro 8 .
Quadro 8. Características relacionadas com a CTC de solos do Estado de Minas Gerais. Características Muito Baixo
Baixo
Classes Médio
Alto
0,61–1,80 1,81–3,60 3,61– 6,00 SB cmolc/dm3 ≤ 0,60 0,21–0,50 0,51–1,00 1,01– 2,00 Al3+ cmolc/dm3 ≤ 0,20 0,81–2,30 2,31–4,60 4,61– 8,00 t cmolc/dm3 ≤ 0,80 (H + Al) 1,01–2,50 2,51–5,00 5,01– 9,00 ≤ 1,00 3 cmolc/dm 1,61–4,30 4,31–8,60 8,61– 15,00 T cmolc/dm3 ≤ 1,60 m% 15,1–30,0 30,1–50,0 50,1– 75,0 ≤ 15,0 20,1–40,0 40,1–60,0 60,1– 80,0 V% ≤ 20,0 FONTE: Comissão de Fertilidade do Solo do Estado de Minas Gerais (1999).
i.
Muito Alto > 6,00 > 2,00 > 8,00 > 9,00 > 15,00 > 75,00 > 80,0
Valor T
A capacidade de troca catiônica (T) é geralmente determinada a pH 7,0, ou a pH 8,2 (para ( para solos alcalinos e salinos). Ultimamente, tem sido mais usado o valor T a pH 7,0 que é calculado somando-se as bases e a acidez total (SB + H + Al). Além Al ém dessas duas expressões, expressões, pode-se ainda citar o valor t ao pH do solo (CTC efetiva), que é calculado somando-se as bases com a acidez trocável (SB + Al 3+).
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2) Os cátions deslocados, bem como o excesso de KCl em solução são eliminados da amostra, por meio de filtração e lavagens. No filtrado, podem ser determinadas as bases Na +, Ca 2+ e Mg2+, que, adicionadas ao K +, determinado em outra extração, dão a soma de bases (SB). Também nesse filtrado determina-se Al3+. Outra alternativa é continuar com a lavagem do excesso de KCl e os seguintes passos: 3) Agita-se a amostra agora com uma solução que contenha outro cátion, CaCl 2 0,5 mol/L, por exemplo:
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no valor da CTC com a elevação do valor do pH foi denominado CTC dependente de pH , como já discutido anteriormente. anteriormente. No pH da solução extratora correspondente ao do solo, tem-se a CTC efetiva, que é a CTC permanente mais o aumento do valor da CTC com a elevação do pH de extração correspondente à CTC pH-dependente até o pH do solo.
ii.
Soma de Bases (SB)
A soma de bases (SB) é calculada somando-se os teores de Ca 2+, Mg 2+, K +, Na + e NH4+ trocáveis. Nos solos ácidos de regiões tropicais, como os do Estado de Minas Gerais, os cátions trocáveis Na+ e NH4+ geralmente têm magnitude desprezível.
SB = Ca 2+ + Mg 2+ + K + + Na + + NH 4 + iii.
Saturação por Bases (V)
A participação das bases no complexo sortivo do solo, expressa em porcentagem, é conhecida como saturação por bases (V). V =
SB x100 T
Para este cálculo, usa-se o valor T (CTC a pH 7,0). OBS: Eutrofismo e Distrofismo: um solo é considerado Eutrófico ou Eutrófico ou Distrófico Distrófico se sua saturação por bases é superior superior ou inferior a 50%, respectivamente.
iv.
Saturação por Alumínio (m)
A saturação por alumínio, representada por m, é calculada pela expressão:
m=
Al 3+
x100
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A acidez trocável é representada pelo Al 3+ mais o H+ que faz parte da CTC efetiva. Como, em geral, a participação do H + é pequena em relação ao Al 3+, este valor é também chamado de alumínio trocável. O alumínio é considerado como acidez porque, em solução, por hidrólise, gera acidez, de acordo com a seguinte equação simplificada:
Al 3+ + 3 H 2O ⇔ Al (OH )3 ↓ +3H + vi.
Acidez Potencial
A determinação da acidez total ou potencial é feita usando-se como extrator uma solução tamponada de acetato de cálcio 0,5 mol/L, pH 7,0. Esta acidez inclui H + Al (H + trocável, H de ligações covalentes que é dissociado com a elevação do pH, Al 3+ trocável e outras formas de Al). A maior parte do H provém das cargas negativas dependentes do pH. Esta fração é chamada acidez dependente do pH. A participação do H em geral é maior do que a do alumínio trocavél.
8.1.2. Fatores que Afetam a Capacidade de Troca Catiônica Muitas condições do solo têm influência sobre a CTC, dentre as quais: pH, natureza dos cátions trocáveis, concentração da solução e natureza da fase sólida. O efeito do pH se verifica, principalmente, sobre as cargas dependentes de pH, como já se discutiu. A natureza dos cátions trocáveis afeta a preferencialidade de troca no solo, de acordo com a densidade de carga dos cátions, isto é, Z/r, onde Z é a carga do íon e r é o raio do íon hidratado. Os cátions que têm maior densidade de carga são mais retidos nas cargas negativas do solo. Por isso, os cátions polivalentes são geralmente mais fortemente retidos no solo (Figura 45). A seqüência de preferencialidade de troca de cátions para uma mesma concentração foi estabelecida por Hofmeister, sendo conhecida como seqüência de Hofmeister (Mengel & Kirkby, 1982), ou série liotrópica (Russel & Russel, 1973). Esta seqüência é a seguinte:
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(Fonte: http www.gly.fsu.edu).
Figura 45. Raio iônico (proporcional) e a carga dos principais íons presentes no solo. O alumínio, sendo trivalente, é mais fortemente retido que os divalentes. O hidrogênio, em razão de suas propriedades específicas, não se comporta como monovalente, quanto à preferencialidade de troca. Seu papel papel depende, também, também, da natureza do do material trocador. A concentração dos cátions na solução do solo afeta a preferencialidade de troca, interagindo com a carga dos cátions envolvidos. Assim, à medida que se dilui a solução, mantendo constantes as quantidades dos cátions presentes, verifica-se um aumento na preferencialidade de troca pelos cátions de menor valência, como o Na +. Em razão disso, em solos de regiões úmidas as bases vão sendo lixiviadas e o cátion que acaba predominando no complexo é o Al 3+; por outro lado, em solos de regiões áridas e semi-áridas a tendência é de acúmulo de cátions monovalentes, principalmente o Na +. A natureza do material trocador influi, principalmente, na densidade de cargas negativas responsáveis pela CTC do solo, que pode ser expressa em cmol kg-1. Em solos de regiões
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A capacidade de troca aniônica é definida como o poder do solo de reter ânions na fase sólida, numa forma trocável com outros ânions da solução. Entretanto, a manifestação desta propriedade não é tão característica quanto à troca catiônica, isto é, não são atendidas tão perfeitamente as condições de rapidez, reversibilidade e estequiometria. Por esta razão, a troca aniônica é mais freqüente e convenientemente denominada adsorção aniônica, sendo a adsorção um processo mais complexo do que a simples troca. Um aspecto particular do comportamento de certos ânions no solo é a adsorção específica. Por este processo os ânions são retidos pela fase sólida, por meio de ligações fortes (covalentes), passando a fazer parte da estrutura da micela, em sua superfície. Este tipo de adsorção é de baixa reversibilidade e é bem conhecido para o fósforo, sendo o principal responsável pela fixação de fósforo no solo, principalmente nos solos ricos em óxidos de ferro e alumínio. Uma reação desta natureza é aqui apresentada de forma simplificada (Mengel & Kirkby, 1982):
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As cargas positivas do solo, responsável pela adsorção aniônica, são, normalmente, dependentes do pH do meio. Diminuindo o pH, aumentam as cargas positivas do solo e a adsorção aniônica também aumenta.
8.3. Dupla Camada Difusa Dupla camada difusa é a denominação dada ao conjunto dos íons que circundam as partículas coloidais em suspensão. Nas argilas silicatadas predominam as cargas elétricas negativas. Estas atraem os íons carregados positivamente, formando uma camada mais concentrada próxima às partículas. Em função da concentração e das características do íon presente, esta camada pode ser mais ou menos espessa permitindo, respectivamente, respectivamente, menor ou maior aproximação entre partículas. Dentre as características do íon que são importantes na definição da espessura da dupla camada estão a valência do íon e o raio iônico hidratado. Maior valência para um mesmo raio iônico produz compressão da dupla camada. De forma análoga, maior raio iônico hidratado para uma mesma valência permite a expansão da dupla camada. A dispersão do solo, efetuada no procedimento de rotina para a determinação dos teores de areia, silte e argila, utiliza os conceitos de dupla camada difusa. No solo, estes conceitos ajudam a compreender fenômenos como a dispersão das argilas, que podem se movimentar no perfil causando o bloqueio bloqueio de poros e mudanças importantes nas propriedades propriedades físicas.
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o ã ç a r t n e c n o C
Figura 46. Distribuição de íons a partir da superfície de colóide eletronegativo, de acordo com o conceito de dupla camada difusa (DCD) (Mitchell, ( Mitchell, 1976). 8.4. Ponto de Carga Zero (PCZ) A superfície dos colóides do solo pode apresentar cargas positivas ou negativas, dependentes ou não do pH do solo. O solo como um todo possui cargas elétricas positivas e negativas simultaneamente. Assim, existe um determinado pH do solo que o número de cargas positivas se equivale ao número de cargas negativas, sendo considerado então o pH do solo em que as cargas são nulas ou ponto de carga zero, sendo característico de cada solo em particular.
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A matéria orgânica do solo apresenta valores baixos de PCZ e quando adicionada a solos muito intemperizados pode se ligar a argilominerias do solo, diminuindo assim, sua carga positivas e o PCZ, PCZ, resultando em um aumento das cargas cargas negativas do solo.
8.5. Dispersão e floculação das partículas do solo O PCZ de um solo pode influenciar muito no processo de dispersão e floculação de um solo, pois quando um solo se encontra próximo ao seu PCZ a repulsão entre partículas é mínima. O PCZ do solo nada mais é que a média de cargas presentes no solo proveniente dos seus diversos constituintes, que em solos com carga variável ocorre na faixa de pH de 3,5-5,0. Assim ocorrerá dispersão das partículas do solo quando o pH do solo for muito maior que o pH em que ocorre o PCZ. Por outro lado, em pH do solo próximo ou abaixo do pH em que ocorre o PCZ de um solo, há um predomínio de cátions que formam complexos fortes, alta concentração de eletrólitos e altos teores de óxidos, ocorre a floculação das partículas, podendo ser desejável para obter-se uma boa estruturação do solo. A floculação da argila é um processo indispensável na formação dos microagregados que por sua vez são transformados em macroagregados macroagregados principalmente por meio da microbiota do solo, que é influenciada pela quantidade e qualidade de MOS. O compartimento ativo, principalmente bactérias e fungos, interage intensamente com a fração argila, que também atua na estabilização de seus metabólitos e produtos de decomposição. Muito desses compostos
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H [ + ] = OH [ − ] =10−7 O pH é definido como o logaritmo do valor de concentração do hidrogênio, com o sinal trocado. Na água pura o pH é, portanto, igual a 7. O aumento da atividade de H + em solução determina valores de pH menores que 7,0, e o aumento dos íons OH - eleva o pH a valores maiores do que 7,0.
pH = -log[H + ] A água presente no solo apresenta sais dissolvidos, colóides minerais e orgânicos e seres vivos em constante atividade. Estes elementos são capazes de alterar direta ou indiretamente o pH. O solo pode também apresentar minerais primários capazes de liberar elementos que afetam o pH. Além disso, a superfície do solo está em contato com a atmosfera, recebendo sua influência. Em se tratando de um sistema aberto, está constantemente recebendo fluxos de matéria, especialmente pelas soluções percolantes ou água que ascende dos lençóis subterrâneos. O balanço final da ação destes diversos contribuintes determina o pH final do solo. Em função de seu pH, os solos podem ser separados em ácidos, neutros ou alcalinos. Em geral, a grande maioria dos solos nas condições tropicais úmidas é ácida. Os solos, com o avanço do intemperismo, tornam-se progressivamente mais ácidos, em função da perda dos cátions alcalinos e alcalino-terrosos (p.e. cálcio e potássio) e da progressiva liberação de alumínio pela degradação das argilas. Solos sob florestas temperadas de coníferas também se acidificam pela
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a) Minerais de Argila i.
íons H+ trocáveis adsorvidos na superfície do argilomineral e que são dissociados a pH baixo (4,0). Esquematicamente Esquematicamente a dissociação dissociação pode ser representada por: por:
ii.
íons Al3+ trocáveis adsorvidos na superfície superfície do mineral de argila que passam passam à solução do solo. O caráter ácido deve-se às reações de hidrólise do Al 3+ hidratado em solução, conforme mostram as reações:
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A oxidação de amônio a nitrato se dá em duas etapas:
A oxidação biológica de compostos orgânicos também produz CO 2, o qual reage com água para formar ácido carbônico, que se dissocia perdendo prótons (H +), de acordo com as reações:
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Os solos geralmente se comportam como ácidos fracos e os metais alcalinos tendem a formar bases fortes. Portanto, em condições de pH neutro, sais formados por esses cátions com ânions provenientes de ácidos fracos tendem a se dissociar para recompor parcialmente o ácido, com o ânion capturando prótons do meio. A fração coloidal do solo, negativamente carregada, comporta-se como o ânion de um ácido fraco. Ex:
[CH 3 − COO ]2 = Ca + 2 H 2O ↔ 2CH 3COOH + 2OH − + Ca 2+ Os metais alcalinos e alcalino-terrosos são constituintes dos minerais primários, cujo intemperismo consome prótons do meio liberando esses cátions (bases trocáveis) na solução, os quais podem, então, ser adsorvidos pela fase sólida.
9.2. Capacidade Tampão da Acidez do Solo A capacidade tampão da acidez dos solos (CTH) é função das características do complexo de troca catiônica, sendo definida como a "resistência que os solos apresentam à
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básicos, se constituindo em outra importante fonte de acidificação progressiva dos solos. O uso de fertilizantes pode ocasionar acidificação do solo, pois em algumas reações eles liberam íons H+ para o meio, podendo formar compostos ácidos, tais como, o HNO 3 e H2SO4. O conjunto desses fatores conduz à acidificação progressiva dos solos, particularmente em regiões tropicais com precipitações que favoreçam a percolação e condições de drenagem que permitam a lixiviação.
9.4. Problemas Causados pela Acidez do Solo A acidez pode trazer problemas diretos e indiretos às plantas, seja pela toxidez direta às plantas ou por afetar afetar a disponibilidade de de nutrientes e elementos elementos tóxicos. O alumínio, conforme já discutido, constitui componente importante da acidez de solos tropicais. O Al+3 em altas concentrações pode ser tóxico às plantas, constituindo uma das principais limitações agrícolas em solos ácidos. Além disso, interfere na disponibilidade de
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aos colóides do solo no lugar dos cátions de caráter ácido. O alumínio é precipitado como hidróxido de baixa solubilidade e o gás carbônico é perdido para a atmosfera.
10. Reações de oxidação e redução no solo Na superfície terrestre predominam as condições oxidantes, em virtude da abundância de oxigênio. Os solos, em sua maioria, refletem esta condição apresentando condições oxidantes. O meio oxidante também favorece a rápida decomposição da matéria orgânica, uma vez que a respiração aeróbia é mais eficiente e rápida que a respiração anaeróbia. Por outro lado, um ambiente redutor pode ocasionar mudanças no comportamento de alguns componentes do solo. Isto ocorre em condições ligadas, principalmente, ao acúmulo de água no solo, decorrente de problemas de drenagem, posição do solo na paisagem ou condições especiais, como a irrigação por inundação permanente. Micro sítios de redução podem ainda ocorrer em solos bem drenados, relacionados a porções onde o oxigênio tem sua difusão limitada
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BIBLIOGRAFIA BIBLIOGRAFIA CONSULTADA ALVAREZ V., V.H. Avaliação da fertilidade do solo. Viçosa. UFV (Notas de aula) 1986. ALVAREZ-PUEBLA, ALVAREZ-PUEBLA, R.A.; GOULET, P.J.G..; GARRIDO, J.J. Characterization of the porous structure of different humic fractions Colloids and Surfaces A: Physicochem. Eng. Aspects 256 (2005) 129–135. ALVAREZ-PUEBLA, R.A.; VALENZUELA-CALAHORRO, C.; GARRIDO, J.J. Theoretical study on fulvic acid structure, conformation conformation and aggregation A molecular modelling approach approach Science of the Total Environment 358 (2006) 243– 254 AMARAL, A. S.; I. ANGHINONI, R. HINRICHS & I. BERTOL Movimentação de partículas de calcário no perfil de um cambissolo em plantio direto. R. Bras. Ci. Solo, 28:359-367, 2004 ASSOCIAÇÃO NACIONAL PARA DIFUSÃO DE ADUBOS. Manual de adubação. E. Malavolta e J. P. Romero (eds.), São Paulo. 346 p 1985. AUTRY, A. R.; FITZGERALD, FITZGERALD, J. W.; Sulfonate S: A major form of forest soil organic sulfur Biology and Fertility
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CHAN, K.Y.; BOWMAN, A.; OATES, A. Oxidizible organic carbon fractions and soil quality changes in an oxic paleustalf under different different pasture leys. Soil Science, Science, Baltimore, v.166, n.1, p.61-67, p.61-67, Jan. 2001. CHRISTENSEN, B.T. Carbon in primary and secondary organo-mineral complexes. In: CARTER, M.R.; STEWART, B.A. (Ed.). Structure and organic matter storage in agricultural soil, Boca Raton: CRC, 1996. p.97165. (Advances in soil Sciences). CIOTTA M.N.; BAYER, C.; FONTOURA, S.M.V.; ERNANI, P.R.; ALBUQUERQUE, J.A. Matéria orgânica e aumento da capacidade de troca de cátions em solo com argila de atividade baixa sob plantio direto. Ciência Rural, Santa Maria, v.33, n.6, p.1161-1164, nov-dez, 2003CIOTTA, M.N.; BAYER, C.; ERNANI, P. R.; FONTOURA, S.M.V.; WOBETO, C.; ALBUQUERQUE, J.A.. Manejo da calagem e os componentes componentes da acidez de latossolo bruno bruno em plantio direto. R. Bras. Ci. Solo, 28:317-326, 2004. CLEVELAND, C.C.; TOWNSEND, A.R.; SCHMIDT, S.K. Phosphorus Limitation of Microbial Processes in Moist Tropical Forests: Evidence from Short-term Short-term Laboratory Incubations Incubations and Field Studies. Ecosystems 5: 680–691, 2002.
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GROHMANN, F. Correlação entre superfície específica e outras propriedades de solos de São Paulo. R. bras. Ci. Solo, I:9-12. 1977. GROHMANN, F. Superfície específica. In: A. C. Moniz (ed.) Elementos de Pedologia. Rio de Janeiro. Livros Técnicos e Científicos Ed. S.A. p. 111-112. 1975. GUPPY, C.N.; MENZIES, N.W.; BLAMEY, F.P.C.; MOODY, P.W. Do Decomposing Organic atter Residues Reduce Phosphorus Sorption in Highly Weathered Soils? Published online August 4, 2005Soil Sci. Soc. Am. J. 69:1405–1411 (2005). HARA, T. Capacidade de troca de cátions de três solos de MInas Gerais. Universidade Federal de Viçosa. 74 p. (Tese de M. S.) 1974. HARWARD, M. E. & REISENAUER. Reactions and movement inorganic soil sulfur. Soil Sci. 101:326-335. 1966. HOGUE, E.; WILCOX, G. E. & CANTLIFFE, D. J. Effect of soil phos phorus levels on phosphate fraction in tomato leaves. J. Am. Soc. Hort. Sci., 95:174-176. 1970. 19 70. ILSTEDT, U.; SINGH, S. Nitrogen and phosphorus limitations of microbial respiration in a tropical phosphorusfixing acrisol (ultisol) compared with organic compost. Soil Biology and Biochemistry, 37, 7, 2005, 1407-1410.
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MENGEL, K. & KIRKBY, E. A. Principles of plant nutrition. 3rd ed. Bern, International Potash Institute. 655 p. 1982. MENGEL, K. Turnover of organic nitrogen in soils and its availability to crops. Plant Soil, 181:83-93, 1996. MEURER, E. J. (Editor). Fundamentos de química do solo. Gênesis, Porto Alegre. 174 p. 2000. MICHEL, K.; MATZNER, E. Nitrogen content of forest floor Oa layers affects carbon pathways and nitrogen mineralization. Soil Biology & Biochemistry 34 (2002) 1807–1813 milho. Horticultura Brasileira, Brasília, v.22, n.2, p.326-331, abril-junho 2004. MITCHELL, J. K. Fundamentals of soil behavior. New York, John & Sons, Inc. 422 p. 1976. MONIZ, A. C. Composição química e estrutura dos minerais de argila, In:Moniz, A. C. (ed.), Elementos de Pedologia. Rio de Janeiro. Livros Técnicos e Científicos, Editora S.A. p. 29-44. 1975. MOREIRA, F. M. S.; SIQUEIRA, J. O. Microbiologia e bioquímica do solo. UFLA, 2002, 625 p. MUNEER, M.; OADES, J.M. The Role of Ca-Organic Interactions in Soil Aggregate Stability. 111. Mechanisms and Models. Aust. J. Soil Res., Res., 1989, 27, 411-23 411-23
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SCHMIDT, M. W. I.; SKJEMSTAD, J. O.; GEHRT, E; KOGEL-KANBNER, I. Charred organic carbon in German chernozemic soils. European Journal of Soil Science, June 1999, 50, 351-365 351-365 SCHNITZER, M.; KHAN, S.U. Humic substances in the environment. Marcel Dekker. 1972.327 p. SCHOFIELD, R. K. Effect of pH on eletric charges carried by clay particles. J. Soil Sci., 1:1-8. 1949. SCHULTEN, H.R.; SCHNITZER, SCHNITZER, M. The chemistry of soil organic nitrogen: a review Biol Fertil Soils(1998) 26:1– 15. SHAW, D. J. Introdução à química dos colóides e de superfície. Tradução: Jergen Heinrich Maar. São Paulo. Editora da Universidade de São Paulo. 185 p. 1975. SILVA, J.; LIMA E SILVA, P.S.; OLIVEIRA, M.; BARBOSA E SILVA, K.M. Efeito de esterco bovino sobre os rendimentos de espigas verdes e de grãos de SIMPSON, A. J.; KINGERY, W. W. L.; HAYES, HAYES, M. H. B.; SPRAUL, SPRAUL, M.; HUMPFER, E.; E.; DVORTSAK, R.; R.; KERSSEBAUM, R.; GODEJOHANN, M.; HOFMANN, M. Molecular structures and associations of humic substances in the terrestrial environment Naturwissenschaften Naturwissenschaften (2002) 89:84–88 SIMPSON, R.T.; FREY, S.D.; SIX, J.; THIET, R.K. Preferential Accumulation of Microbial Carbon in Aggregate