The effect of chromium in textile industry waste on soil quality in karanganyar indonesia

THAI NGUYEN UNIVERSITY UNIVERSITY OF AGRICULTURE AND FORESTRY AYU MONICA ENDRINA TOPIC TITLE : THE EFFECT OF CHROMIUM IN TEXTILE INDUSTRY WASTE ON SOIL QUALITY IN KARANGANYAR, INDONES

THAI NGUYEN UNIVERSITY

UNIVERSITY OF AGRICULTURE AND FORESTRY

AYU MONICA ENDRINA TOPIC TITLE :

THE EFFECT OF CHROMIUM IN TEXTILE INDUSTRY WASTE ON SOIL

QUALITY IN KARANGANYAR, INDONESIA

BACHELOR THESIS

Study Mode : Full-Time

Major : Environmental Science and Management

Faculty : International Programs Office

Batch : 2014 – 2017

Thai Nguyen, November 2017

DOCUMENTATION PAGE WITH ABSTRACT

Thai Nguyen University of Agriculture and Forestry

Degree Program : Bachelor of Environmental Science and Management

Student Name : Ayu Monica Endrina

Thesis Title : THE EFFECT OF CHROMIUM IN TEXTILE

INDUSTRY WASTE ON SOIL QUALITY IN KARANGANYAR, INDONESIA

Foreigner Supervisor (s): Prof Dr Samanhudi, S.P, M.Si

Dr Ir Margaretha Maria Alacoque Retno Rosariastuti, M.Si

Vietnamese Supervisor Dr Hồ Ngọc Sơn

Abstract: Chromium exists in the environment in several diverse forms such as, Cr (III), and Cr (VI) Cr toxicity depends on its valence state Cr (VI) which is regarded as being highly mobile is toxic, while Cr (III) is less mobile and less toxic Cr (VI) being more mobile in soil, more toxic and a stronger oxidant penetrates more readily into the cell membranes than the trivalent form Chromium affects to the soil pH, N total of the soil, and also K exchangeable This study was conducted by taking samples from five locations (Soil from the field, water bodies and irrigation), which four locations were in a location in textile industries area surrounding them such as Macanan, Getas, Waru, Ngringo and one location was in

a location with no textile industry such as Karangpandan After obtaining the sample we analyzed soil chemical characteristic (pH, N total, P available, K exchangeable, C-organic, electric conductivity and cation exchange capacity) in the Laboratory of Chemistry and Soil Fertility, also about biological characteristic (indigenous bacteria and fungi) in the Laboratory of Soil Biology and Biotechnology The data were analyzed by statistical analysis using T-test 95%,

and tested the correlation to see the effect of chromium on soil quality The result

of this research is at five sampling sites, soil at five locations contain the chromium content Three locations contain chromium exceeds the threshold (>2.5 µg.g-1) ie Getas (5.21 µg.g-1), Karangpandan (3.23 µg.g-1), Ngringo (3.06 µg.g-1) and two sites have chromium content below the permitted threshold (<2.5 µg.g-1) ie Macanan (2.27 µg.g-1) and Waru (2.02 µg.g-1) Karangapandan area which there’s

no industrial factory still contaminated above the threshold, allegedly due to excessive chemical usage such as fertilizer and pesticide The amount of chromium

in the soil will influence to pH of the soil, N total, K exchangeable and also impact

on bacteria but is negatively correlated with the fungi As we know from the data that we have got, the data of chromium the highest is Getas (5.21 µg.g-1) and the lowest is Waru (2.02 µg.g-1), for pH of the soil, Getas (6.96) and Waru (6.00), N total of Getas (0.33%) and for Waru (0.25%), and also for K of Getas (0.24 cmol(+).kg-1) , and for Waru (0.30 cmol(+).kg-1) The data shows how chromium influence several parameters and how it impact the soil quality

Keywords: Chromium, chromium effect, chemical characteristics,

biological characteristic, water quality

Number of Pages: 43 pages

Date of Submission:

Supervisor’s signature

ACKNOWLEDGEMENT

From bottom of my heart, I would like to express my deepest appreciation to all those who provided me the opportunity to complete this research

First and foremost, I would like to express my sincere gratitude and deep regards

to my lovely supervisors: Prof Dr Samanhudi, S.P, M.Si and Dr Ir Margaretha Maria Alacoque Retno Rosariastuti, M.Si as my supervisors from Sebelas Maret University, Surakarta, Indonesia who kindly assisted me with the topic is “The Effect of Chromium in Textile Industry Waste on Soil Quality in Karanganyar, Indonesia” Thanks for your patient with my knowledge gaps and in guiding me whole heartedly when I implemented this research

I also want to express my thanks to Hồ Ngọc Sơn, Ph.D, as the Vietnamese supervisor, for his supervision, encouragement, advice, and guidance in writing this thesis

Besides my supervisors, I would like to thank Mr Sudarsono from the Laboratory

of Soil Biology and Biotechnology, Mr Muzayin from the Laboratory of Chemistry and Soil Fertility, and Mrs Tumisih from the Laboratory of Physics and Soil Conservation Faculty of Agriculture, Sebelas Maret University, Surakarta for providing me an additional knowledge about the soil chemical characteristic (pH, N total, P available, K exchangeable, C-organic, electric conductivity and CEC (cation exchange capacity), also biological characteristic (indigenous bacteria and fungi)

In addition, formal thanks should be offered to the Rector of Sebelas Maret University, Prof Dr H Ravik Karsidi M.S for granting my internship acceptance

I would also like to acknowledge with much appreciation to the Dean of Faculty of Agriculture in Sebelas Maret University, Prof Dr Ir H Bambang Pujiasmanto, M.S who gave the permission to use all required equipment and the necessary materials to conduct

my research in Sebelas Maret University

I wish to thank the staff who work in Balai Penelitian Lingkungan Pertanian (Department of Agricultural and Environmental Research Center), for their help in

chromium analysis, Asep Kurnia, S.P, M.Eng as a Technical Manager of this Department Without them, this research could not be accomplished on time

My sincere thanks also go to this special person Danang Taruno for guiding and helping me finish this study also for his invaluable support and encouragement when I stayed in Solo

Of course, I would like to thank to others Student from Agrotechnology called

“Marmut 2013” from Faculty of Agriculture who very kindly and support me during conduct my internship in Sebelas Maret University

Finally, special thanks to my family (My lovely father and mother also my brother and sister), for their accommodation such as money, for their attention, their love and moral support throughout my study

Surakarta, 20 th June, 2017

Student

Ayu Monica Endrina

TABLE OF CONTENTS

ACKNOWLEDGEMENT 4

PART I INTRODUCTION 10

1.1 Background and Rationale 10

1.2 Objective of Research 11

1.3 Research Questions and Hypotheses 11

1.3.1 Research Question 11

1.3.2 Hypotheses 11

PART II LITERATURE REVIEW 12

2.1 Chromium 12

2.2 Cation Exchange Capacity 12

2.3 Level of Acidity (pH) 13

2.4 C-Organic 14

2.5 N Total 15

2.6 P Available 15

2.7 Exchangeable K 16

2.8 Fungi 16

2.9 Indigenous Bacteria 17

2.10 Water Quality 17

PART III MATERIALS AND METHODS 19

3.1 Time and Place 19

3.2 Equipment 19

3.3 Materials 19

3.3.1 Chemical Characteristic 19

3.3.2 Biological Characterictics 20

3.4 Methods 20

3.4.1 Determination of the Technique Population and Sample 20

3.4.2 Techniques of Collect the Data 20

PART IV RESULT 27

4.1 Chromium on Soil and Water 27

4.2 Soil Chemical Characteristic 27

4.3 Soil Biological Characteristic 29

4.4 Irrigation Water Quality 29

PART V DISCUSSION AND CONCLUSION 31

5.1 Discussion 31

5.1.1 Chromium 31

5.1.2 Soil Chemical Characteristic 32

5.1.3 Soil Biological Characteristic 34

5.1.4 Water Quality 36

5.2 Conclusion 39

REFERENCES 40

LIST OF TABLES

Table 1 Variable Observation of Research 21

Table 2 Chromium Total on Soil 27

Table 3 Chromium Total on Water 27

Table 4 pH Soil 27

Table 5 N Total 28

Table 6 P Available 28

Table 7 K Exchangeable 28

Table 8 Capacity Exchange Cation 29

Table 9 C-Organic 29

Table 10 Indigenous Bacteria 29

Table 11 Fungi 30

Table 12 Electric Conductivity Irrigation 30

Table 13 pH Water 30

LIST OF FIGURES

PART I INTRODUCTION

1.1 Background and Rationale

Karanganyar is one of the districts in Central Java, next to the city of Solo Karanganyar is also one of districts in Central Java which included developing areas Karanganyar, in 2005 has 60 industries comprising textile industry, plastic industry, wood processing industry, oil industry paint, industrial monosodium glutamate, sodium cyclamate industry, industrial, basic chemicals, food and beverage industries Industries that make up the majority in Karanganyar area is textile industry (Nurhayati, 2010)

Textile needs in human life itself is one of the primary needs other than food and shelter, so we need a lot of textile factories to adequate human needs In this case,

it is becoming counter when viewed from the other side of Karanganyar which is also famous as an agricultural area Sometimes a lot of factories were found immediately adjacent to the land of the farmer Each phase of the production of textiles, requiring chemical compounds containing heavy metals Heavy metal means such as Cr (chromium), Cd (cadmium), and Hg (hydrargyrum) The problems that became the main focus when the all of the factories has not been a standard in the management of textile waste Waste that is not managed well, dumped out into the water and finally entered agricultural land belonging to citizens As a result of agricultural land in the region has contamination levels of chromium in the range between 2.13 µg.g-1 to 7.43 µg.g-1 (Junaedi, 2004)

This is the main reason of this research paper According to USDA (2001) soil quality is the capacity of a specific kind of soil to function, within natural or managed ecosystem boundaries, to sustain plant and animal productivity, maintain or enhance water and air quality, and support human health and habitation The research would like to study the effect of textile wastes, especially chromium heavy metals to soil by chemical and biological aspects as assessment parameters For comparison this research also will take samples in areas that are free of the indicated textile wastes Further elaboration would be discussed in the contents of this thesis

1.3 Research Questions and Hypotheses

1.3.1 Research Question

The research aims to answer the following question;

What is the effect of chromium in textile waste on the soil quality in Karanganyar?

1.3.2 Hypotheses

This research includes 2 hypotheses such as:

1 Null hypotheses of this research: chromium in textile industry waste is affecting on soil quality in Karanganyar, Indonesia

2 Alternative hypotheses of this research: chromium in textile industry waste is not affecting on soil quality in Karanganyar, Indonesia

PART II LITERATURE REVIEW

Trivalent chromium is weakly soluble in highly acid and alkaline soils, whereas hexavalent Cr dissolves well in acid and alkaline soils Cr (VI) in soil is reduced to Cr (III), which is not well available for plants Chromium (VI) has a harmful effect on soil microorganisms by depressing their biological activity Like other heavy metals, chromium may influence the enzymatic activity of soils by affecting soil microorganisms as well as by modifying the environment in which they live, and which is rich in many enzymes (Barabasz et al., 1998)

2.2 Cation Exchange Capacity

Cation exchange capacity (CEC) is a parameter of soil which represents the capability of soil to attract, retain and hold exchangeable cations (K+, Na+, Ca2+,

Mg2+, Al3+, etc) Many soil parameters influence the soil exchangeable capacity especially soil pH, soil texture, and organic matter content up to a certain extent

Soil pH is an important soil parameter which is positively correlated with CEC (Foth, 1990) High content of organic matter and clay conduces to the higher CEC values because both have a large number of negative charges on their surface which attract and hold cations

Negative charges of soil particles are the result of isomorphic substitutions

in phyllosilicate structures, non-compensated bonds at the edges of reticular plans,

or dissociation of functional organic groups (Pansu and Gautheyrou, 2006) Cation exchange reactions in soils occur mainly near the surface of clay and humus particles, called micelles (Foth, 1990) Cations from the soil surface can be quite easily exchangeable with the cations from the solution

2.3 Level of Acidity (pH)

Acidity of soil means that the hydrogen ion (H+) and aluminum ion (Al3+) concentration of the soil is high while alkalinity implies that their concentrations are low Again the Solubility of mineral nutrients is greatly affected by soil pH, phosphorous is never readily soluble in the soil but is most available in soil with a

pH range that centered around 6.5 Extremely and strongly acidic soils (pH 5.0) can have high concentration of soluble aluminum (Al3+) ion and manganese, which may be toxic to the growth of some plants A pH range of approximately 6-7 promotes the most readily available plant nutrients, while a pH above 7 (alkaline) reduces the ability of plants to absorb elements such as iron, manganese, boron, and other trace elements (Tisdale et al.,1993)

4.0-Acidity also affecting a lot of things such as CEC (Cation Exchange Capacity) which is affect the balance of the cations, K, Na, Ca, Mg Acidity also affect the population of microorganism The most favorable acidity for microorganism is around 6.6 to 7.3 that contribute to the availability of nitrogen, sulfur, and phosporus in soil The existence of heavy metal affected by soil acidity Higher pH will increase the existence of heavy metals, lower pH will makes the heavy metals more soluble in the water and can be loss by bioremediation technique (USDA, 1998)

2.4 C-Organic

C-organic is a determinant of soil productivity and also being a food source

of microorganisms in the soil by the chemical reactions At the time of land formation, many organic materials contribute as mineral materials, such as the results of fungi metabolites in the soil, as though calcium salt and in groundwater

as the next dissolved mineral available for plants (nutrients) But the process is very complex, as do the organometallic compounds Fe and Al (Fauzi, 2008)

A lot of advantages of organic matter such as increase nutrient storage and release, increase microbial enhancement of nutrient availability, increase the amount of cation exchange capacity, increase sorption of organic compound, increase anion sorption, decrease and increase metal mobility, soil pH buffering and amelioration, growth-regulating substances SOM also affects the mobility of heavy metals that may serve as plant nutrients (e.g, Zn) or may not (e.g, Cd) Addition of organic matter to soil can either decrease or increase metal availability, solubility, and plant uptake Insoluble organic matter usually forms insoluble organometal complexes or sorbs metal ions, making them less available for plant uptake or leaching (Sauve et al., 1998)

However, many organic amendments have a soluble C component or produce soluble decomposition product, and the soluble organic matter can increase metal solubility by forming soluble organometal complexes (Alvarez et al., 1999) The influence of SOM on metal mobility can also be modified by the

pH solution (Yoo and James, 2002) In addition to these effect, SOM affect the mobility of some metals because decaying organic matter stimulates reducing conditions as microorganisms deplete the soil oxygen supply and reduce other electron acceptors Among plant nutrients, manganese (Weil, 2000) and iron (Childers et al., 2002) are especially prone to increased solubility under reduced conditions In contrast decomposable organic matter (such as manure) can reduce the solubility and toxicity of chromium by reducing the toxic Cr (IV) to the nontoxic, much more immobile Cr (III) form (Losi et al., 1994)

2.5 N Total

Total Nitrogen is an essential nutrient for plants and animals However, an excess amount of nitrogen in a waterway may lead to low levels of dissolved oxygen and negatively alter various plant life and organisms Sources of nitrogen include: wastewater treatment plants, run off from fertilized lawns and croplands, failing septic systems, runoff from animal manure and storage areas, and industrial discharges that contain corrosion inhibitors (USDA, 2013)

The functions of nitrogen total in plant and animal life are many Essentially all life processes depend directly on it Nitrogen occurs chiefly as protein and nucleoproteins with smaller and widely varying amounts of amines, amino acids, amino sugars, polypeptides, and many miscellaneous compounds (Allison, 1957)

A lot of primary nutrient contains textile industry waste, such as N, P, K which compared with common organic manures and chemical fertilizers The amount of N present in textile industry waste was always higher than all organic manures, around 1.758% Even though P percentage was usually low, around 0.26%, however the amount was comparable with the amount in compost The amount of K is lower than any of the organic fertilizer, it’s around 0.338% Nevertheless the amount was better compared to zero K found in chemical fertilizer (Maddumapatabandi et al., 2014)

2.6 P Available

Soil phosphorus (P) deficiency is one of the major factors limiting crop yields worldwide Although required by plants in a smaller quantity compared with other primary macronutrients (e.g nitrogen and potassium) the inadequate supply

of P results in severe limitations to plant growth (McLaughlin, 2015)

Many function of Phosphorus, such as in photosynthesis and respiration, P plays a major role in energy storage and transfer as ADP and ATP (adenosine di- and triphosphate) and DPN and TPN (di- and triphosphopyridine nucleotide), P is part of the RNA and DNA structures, which are the major components of genetic information, P aids in root development, flower initiation, and seedand fruit

development, and also P has been shown to reduce disease incidence in some plants and has been found to improve the quality of certain crops (Uchida, 2000)

The quantities of plant-available and non-available K in the soil vary greatly amongsoil types, and dynamic equilibrium reactions exist between the different pools of soil K Thus, a number of soil physical and chemical properties as well as plant soil interactions and soil microbial activities affect the fixation and release of

K in soils (Peiter et al., 2013)

2.8 Fungi

Soil fungi are microscopic plant like cells that growing long threadlike structures or hyphae that make amass called mycelium The mycelium absorbs nutrients from the roots it has colonised, surface organic matter or the soil It produces special hyphae that create the reproductive spores Some fungi are single celled (e.g yeast) Fungi have many different structures but they can act in similar ways and thusare not as plant specific in their needs as some soil bacteria such as

Rhizobia (Jenkins, 2005)

Fungi perform important services related to water dynamics, nutrient cycling, and disease suppression Along with bacteria, fungi are important as decomposers in the soil food web, converting hard to digest organic material into usable forms There are several things you can do to encourage fungi in your soil such as provide a hospitable environment, reduce tillage, reduce fungicide use, and growth plants that encourage mycorrhizal fungi (Hoorman, 2011)

2.9 Indigenous Bacteria

The soil bacterial community is under the constant influence of its environment Indigenous bacteria are beneficial fiber degrading bacteria can be used to support agricultural technology in the field of microbiology That effect of indigenous microorganisms (IMO’s) on the native soil was investigated in the present study Supplementation of IMO’s suspension to the soil alters the physico-chemical, biological and enzyme properties of the soil These alternations include decreases in pH from 7.2 to 6.8; increase in electrical conductivity 0.36 to 1.21 μmohs.cm-1

, water holding capacity 0.36 to 2.2 ml.g-1 of soil of control and test soils respectively There is increase in soil texture like clay, phosphorous and potassium in the test soil Enzyme activities such as protease and urease were assessed in both the soil samples with and without amendment of respective substrates (casein and urea) Accumulation of hydrolytic products tyrosine and ammonia from the substrates in the soil was estimated at periodic intervals Protease and urease enzyme activities were relatively higher in soil amended with IMO’s and respective substrate than control (Narasimha et al., 2012)

Factors affecting growth of indigenous bacteria is environment factors such

as temperature and pH Microorganisms can be found in a wide range of temperature From the cold of the Arctic to the near-boiling environments of geysers Depending on the different temperature regimes, these bacteria have different temperature relationships with cardinal points (minimum, optimum, maximum) related to the environmental conditions but for pH has a determining role in the type of microorganisms that predominate in different soil (Pettersson, 2004)

2.10 Water Quality

Water quality is a term used here to express the suitability of water to sustain various usesor processes Any particular use will have certain requirements for the physical, chemical orbiological characteristics of water; for example limits

on the concentrations of toxic substances for drinking water use, or restrictions on

temperature and pH ranges for water supporting invertebrate communities Consequently, water quality can be defined by a range of variables which limit water use Although many uses have some common requirements for certain variables, each use will have its own demands and influences on water quality

(Meybeck et al., 1989)

Problems with water quality may be chemical (for example, acidic or alkaline water or concentrations of certain elements) or physical (for example, plant growth such as algae) Some problems may be more obvious than others, and some may require more extensive treatment Water quality can affect plants, soils, livestock, irrigation equipment, domestic use and general farm activities Water quality problems may affect a range of uses, or be restricted to more specific uses Water quality issues and methods of treating them such as pH, iron, hardness, corrosion, salinity, sodicity, turbidity, algae, colour, taste, odour, bacterial growth (Department of Primary Industries, 2014) The industry generates huge amount of waste water contains toxic pollutants Several treatment technologies are using now days with high efficiency and from the present study it was found that advanced oxidation process is very effective in terms of pollutan

PART III MATERIALS AND METHODS 3.1 Time and Place

The research was conducted from March 2017 until July 2017 in Bangsri, Karangpandan (70 37’ 10,308’’ S 1110 1’ 51,316’’ E) as a control (no textille industry) Waru, Kebakkramat (70 30’ 35,788’’ S 1100 54’ 21,456’’ E); Ngringo, Jaten (70 33’ 11,255’’ S 1100 52’ 47,273’’ E); Getas, Jaten (70 34’ 37,319’’ S 1100 54’ 4,014’’ E); and Macanan, Kebakkramat (70

32’ 38,004’’ S 1100 55’ 0,098’’ E) with the land that passed by the stream of waste textile factory and this research was conducted in Laboratory of Chemistry and Soil Fertility, Laboratory of Physics and Soil Conservation, and the Laboratory of Soil Biology and Biotechnology, Faculty of Agriculture, Sebelas Maret University, Surakarta and Department of Environmental and Agriculture Research, Pati

3.2 Equipment

The following materials and equipment were used for the research For collection and processing of the samples for analysis as trowel to take the soil samples, the transparent plastic, paper labels, pens, and the hoes was used The equipment for laboratory analysis are analytical balance 3 decimal, shaker tube, dispenser, test tubes, tube centrifuge, tube of Kjeldahl, the erlenmeyer, distillation flask, watch glass, measuring cups, funnels, Whatman filter paper, measure pipette, AAS (Atomic Absorption Spectrometer), disgest tube, 250 ml boiling flask, autoclave and heating

3.3 Materials

3.3.1 Chemical Characteristic

Chemical characteristic such as chromium, pH, C-organic, N total, P available, K exchangeable, cation exchange capacity, need materials such as concentrated H2SO4; K2SO4 : CuSO4 (20:1); concentrated NaOH; HCl 0,1 N; Olsen extract; ammonium acetate; NaCl 10%; K2Cr2O7; HNO3; HClO4

3.3.2 Biological Characterictics

Biological characteristic such as indigenous bacteria and fungi, need material such as NA media (Nutrien Agar), PDA media (Potato Dextrose Agar), aquadest

3.4 Methods

3.4.1 Determination of the Technique Population and Sample

Determination the point of observation was done intentionally (purposive sampling) by the information that we found about the location of some of the textile factory that passes by the rice fields area and the areas without a textile factory and indicated free of heavy metals The location adjacent to body of water passed by factory waste will be used as an observation point

Figure 1 Sketch (Samples of the Soil)

3.4.2 Techniques in the Collection of the Data

Primary data will collected with the implementation in the field and laboratory analysis Implementation consist of among others the preparation and implementation of the survey The preparation phase includes the preparation of tools, materials and all the tools that support the implementation

of the research As soon as all the stages of preparation tools and materials was complete, the next is the preparations for surveying to determine the location of

the plot, sampling, physical analysis methods and the area that we will do

observation

There are are several steps in the implementation of the land survey indicated that land contain heavy metals due to the textile industry First looking for information about the where abouts of the textile industry and land are estimated not contaminated by the textile industry in of Karanganyar After receiving the information, the next step is to determine the location to be a comparison of contaminated soil and uncontaminated soil to the existence of microorganisms Soil samples will be taken with a zig-zag and distinguish between biological samples and soil samples will be analyzed the chemical content, physics, and biology Then take the irrigation water around the fields

to be analyzed in the laboratory

Table 1 Variable Observation of Research

1 Soil Chemical CEC Titration HCl

10 Soil Physics Soil Moisture Gravimetric %

11 Water Quality Electric

1 Soil Chemical Analysis

a) Cation Exchange Capacity

Measure or weigh the air-dried soil samples 0.5 mm 5 gram and then put it into the bottle shake Add 50 ml of ammonium acetate after it was shaken for 30 minutes and then filter with a Whattman filter Washing with 15 ml of alcohol and discarded Wash with 10% of NaCl and then take 50 cc Distilling

by adding NaOH 5 ml Preparing the container solution 10 ml of boric acid and wait up to 40 ml After the titration with 0.1 N of HCl until the yellow is clean

CEC (cmol (+) kg -1 ) = (Vc - Vb) x N HCl x 0.1 x 1.000 g / 5 g x fk

b) C-organic

Measure air-dried soil samples 0.5 mm with amount around 0.25 gram Then add 2.5 ml of K2Cr2O7 and H2SO4 as much as 3.75 ml Shake homogeneous for 30 seconds Add distilled water until the flask tera limit 50

ml The next day measure the absorbance of the clear solution with a spectrophotometer at wavelength around 561 nm

d) Soil Cr total

This analysis using wet digestion method HNO3 and HClO4 Conscientious weigh 1 g air-dried soil samples < 0.5 mm into the digest tube, add 4 ml of nitric acid p.a, left one night The next day heated with 100° C for 1 hour 30 minutes, leave it until cool and add again 2 ml of nitric acid p.a and 2

ml of perchloric acid p.a Then heated with 130oC for 1 hour, increase the temperature to 150oC for 2 hours 30 minutes (until the steam yellow exhausted,

if there is still steam yellow so add more times), after steaming yellow

exhausted the temperature raised to 170oC for 1 hour, then the temperature is increased be 200oC for 1 hour (until white steam) The destruction is complete with the formation of a white sediment or the rest the clear solution around 1

ml The extract is cooled and then diluted with distilled water to 20 ml, then shaken until homogeneous, leave it overnight Once destruction is complete, the next sample be taken to the Laboratory of Agricultural Environment Research Institute in Pati, Central Java after that perform calculations on the data that has been obtained

Levels of heavy metals Cr (ppm)

P 2 O 5 levels available (ppm)

= ppm curve x ml of extract / ml 1.000 x 1.000 g (g of sample)-1 x fp x 142/190

x fk

g) K available

Weigh the soil 5 gram Adding ammonium acetate 50 ml and shake for

30 minutes Extracting and take 5 ml Add distilled water to a volume of 25 ml Shooting with flamephotometer

Levels K available

= (ppm curve / bst cation) x ml of extract / ml 1.000 x 1.000 g (g of sample) -1 x 0.1 x fp x fk

Information:

ppm curve = levels sample obtained from the curve of the relationship between

the levels of the standard series with its readings after correction for the blank

0.1 = conversion factor from m.e to cmol (+)

bst cations = equivalent weight of K: 39

fp = dilution factor (if any)

fk = correction factor is the water content = 100 / (100 +% moisture content) 2) Analysis of Soil Biology

a) Bacteria

Prepare the tools and materials The media that will we use is NA media (Nutrient Agar) for Bacteria Sterilization in the workplace and the media Make the soil samples becomes more dilute to 10-12 Wait 2 days for incubation and do calculations with the hand colony counter

b) Fungi

Prepare the tools and materials The media that we will use PDA media (Potato Dextrase Agar) for Fungi.Sterilization in the workplace and the media Make the soil samples becomes more dilute to 10-4 Wait 2 days for incubation and do calculations with the hand colony counter

3) Analysis of Soil Physics

a) Levels of Moisture

Level of the moisture will observe to calculate N, P, K soil and organic matter We will do observations with the Gravimetry method First weigh the the empty weighing the bottle (a) Second, weigh the-dried soil samples 0.5 grams and put it into a weighing the bottle, weighing the bottle and soil samples (b) Oven for 4 hours at a temperature 105ºC Cool off in the eksicator and than weighing the bottle (c)

4) Irrigation Water Quality

a) Electricity Conductivity Water Irrigation and Water Body

Wash the electrode with the distilled water and drying with the tisue before measurement of each sample / buffer solution Add the electrode into the sample (approximately 25 ml) read after steady Rinse electrode with the distilled water and dry well with the tissue before measuring the sample / buffer solution

b) Cr Water Irrigation and Water Body

Measuring extracts filtrate, clear water directly with the AAS tool The extract used for the measurement of heavy metals Cr for the ppm of concentration levels using AAS method

Cr level (ppm) = ppm x fp curve

Fp = the dilution factor

c) pH Water Irrigation and Water Body

Adjust the dial (temperature) on the pH gauges with the temperature of solution we checked Calibrating pH-meter with the buffer solution of pH 7.00 Wash the electrode with the distilled water and drying with the tisue before measurement of each sample / buffer solution Add the electrode into the

sample (approximately 25 ml) read after steady Rinse electrode with the distilled water and dry well with the tissue before measuring the sample / buffer solution

5) Data Analysis Method

We did the analysis of the data after we collect all of them, either primary data and secondary data The data that will we take is the chemical and biological soil data, irrigation water and metal content of in fertilizers Data was analysed by statistical analysis using T test, correlation-test by SPSS software

PART IV RESULT

4.1 Chromium on Soil and Water

Table 2 Chromium Total on Soil

Table 3 Chromium Total on Water

Irrigation (µg.L-1)

Cr Total on Water Body (µg.L-1)

Location K Exchangeable cmol(+).kg-1

Table 8 Capacity Exchange Cation

4.3 Soil Biological Characteristic

Table 10 Indigenous Bacteria

Location Bacteria (log 10 CFU.g-1)

4.4 Irrigation Water Quality

Table 12 Electric Conductivity Irrigation

Location EC Irrigation (mS) EC Water

Note : Testing with Independent T-test, Karangpandan as a control, confidence interval 95% Letter a (same with control), b different with control Classification: Based on FAO (1976) * (Good), ** (Enough), ***(Bad) Table 13 pH Water

PART V DISCUSSION AND CONCLUSION

5.1 Discussion

5.1.1 Chromium

Based on the survey results, from five locations there are three locations contaminated with heavy metals including control region which is actually situated on the slopes of the mountain, without any industrial wastes, and water quality was very good Table 1 shows area in the sequential location of the most polluted which is in Getas area (5.21 µg.g-1), Karangpandan (3.23 µg.g-1), Ngringo (3.06 µg.g-1), Macanan (2.27 µg.g-1), and Waru (2.02 µg.g-1) Fourth locations except Karangpandan, located in an area adjacent to the textile mills and sewage to be around the paddy fields so that some contaminated Rice fields Karangpandan contaminated with chromium but viewed from the side of irrigation water and in water bodies showed good quality pH 6.63-6.97 (good) and electrical conductivity 0.1493-0.1471 mS (good) Allegedly it is due to excessive use of chemical fertilizers and pesticides in the surrounding farming activities (Erfandi and Ishak, 2014)

Figure 2 Rice field Area of Getas

The rice field in Getas is located in the middle of the housing area, besides the garbage dump, and next to the textile factory When viewed from the water, the Getas irrigation can still be tolerated from <0.001 µg.L-1, neutral pH and excellently electrical conductivity However, at the disposal of

sewerage, the quality is very bad although in table 2 of chromium in water

<0.001 µg.L-1, pH 8.4 and very high electric conductivity of 3.13 mS High electrical conductivity indicates the high content of ions in the water and very dangerous when polluting rice fields The highest level of chromium getas is 5.21 µg.g-1

This is exacerbated by the proximity of landfills and the use of waste water during the dry season to irrigate the rice fields of the society It should be noted for several industrial areas such as Macanan that irrigation water quality and water bodies look mixed, although it has low chromium levels but must be careful with other metal content such as Pb, Cd, etc Based on the results of the correlation test, Cr soil has a positive correlation for the electric conductivity in the body of water (r=0.829) the flow of factory waste The higher of electrical conductivity will show the number of cations present in the water even though the results of Cr analysis on water show <0.001 µg.L-1 (Valente et al., 2012)

5.1.2 Soil Chemical Characteristic

Heavy metals in small quantities can contaminate the environment and can make it toxic The entry of heavy metals in the soil inhibits the absorption

of nutrients in the soil during the process of plant growth Huffman and Allaway (1973) chromium are very toxic to plants and affect the growth although some plants are not affected by low concentrations of Cr Shanker et al., (2005) explains that some of the effects of chromium on soil nutrients In soybean, Cr (VI) reduces the absorption of K, Mg, P, Fe, and Mn

The order of the polluted locations, there are Getas (5.21 µg.g-1), Karangpandan (3.23 µg.g-1), Ngringo (3.06 µg.g-1), Macanan (2.27 µg.g-1), and Waru (2.02 µg.g-1) Chromium has strong relationship with soil pH (r=0.541) The higher of chromium content it means higher of the soil

pH Notohadiprawiro (2006) explains that high soil pH causes heavy metals to precipitate and will accumulate when supplied continuously Soil acidity level also has a very strong relationship, especially in water bodies namely electrical

conductivity (r=0.783) and pH of water body (r=0.774) For example, the farmers of Getas Village who use factory waste as a substitute for irrigation water during the dry season with electrical conductivity 3.13 (poor) and pH 8.4 have a total Cr content 5.21 μg.g-1

N total from T test result, the highest is Getas (0.33 %) and the lowest is Ngringo (0.22 %) After the correlation tested, chromium has a moderate relationship (r=0.467) This is allegedly due to the use of urea and Cr simultaneously for the dyeing of textile fabrics According to Supriyadi (2004) waste water from the production usually contains a lot of nitrogen because it uses urea to mix the dye For example comparison Cr content of Getas 5.21 μg.g-1 and Ngringo 3.06 μg.g-1

Organic matter has a strong relationship with N total (r=-0.521) and has

a very strong relationship with available P (r=-0.765) The higher of organic matter it means content of N total will be lowest and the lower of N total is the higher of P available Allegedly in these fields indicate organic material that has not decomposed further This causes of it such as a high level of C/N ratio Organic matter is a source of nutrients and energy for microorganisms The availability of nutrients for these microorganisms will have any impact on the process of reproduction of high microorganisms, so that the increasing microorganisms of organic matter decomposition process is increasing and affect nutrient availability (Touratier et al., 1999) For example Ngringo ,the highest of P available content 9.55 ppm, c-organic 2.34 %, N total 0.22 % In Getas, the lowest of P available 8.8 ppm, organic C 1.18 %, N total 0.33 %

K exchangeable after we analysis with T-tested from the different location, and the result shown the highest is Ngringo 0.567 cmol (+).kg-1 and the lowest is Getas 0.239 cmol (+).kg-1 Chromium has a negative correlation with, the levels of Exchangeable (r=-0.480) the higher of chromium it means the lower of K Exchangeable because interactions in the soil are always antagonistic (Rosmarkan and Yuwono, 2002) shown by the data that we